WO2020218558A1

WO2020218558A1 - Compound, material for organic device, composition for forming light-emitting layer, organic field-effect transistor, organic thin-film solar cell, organic electroluminescent element, display device, and illumination device

Info

Publication number: WO2020218558A1
Application number: PCT/JP2020/017800
Authority: WO
Inventors: 琢次畠山; 靖宏近藤; 亮介川角
Original assignee: 学校法人関西学院; Jnc株式会社
Priority date: 2019-04-26
Filing date: 2020-04-24
Publication date: 2020-10-29
Also published as: JPWO2020218558A1; CN113784972A; KR20220004116A

Abstract

Provided is a compound having at least one structure represented by formula (i), as a material used in an organic EL element or other organic device. In formula (1): rings A, B, and C each independently represent an aromatic ring structure; at least one ring member element in at least one of rings A, B, and C is bonded to a partial structure (D); Y is B, P, P=O, P=S, or Si-R'; X¹ and X² are each independently >O, >S, >N-R', >C(-R')₂, or >Si(-R')₂; Q in the partial structure (D) is a single bond, >O, >S, >C(-R')₂, or >Si(-R')₂; the dashed line part is a bonding site; R²¹ through R²⁸ in the partial structure (D) are each independently a hydrogen atom or a specific substituent; and R' is an aryl group or the like.

Description

Compounds, materials for organic devices, compositions for forming light emitting layers, organic field effect transistors, organic thin-film solar cells, organic electroluminescent devices, display devices, and lighting devices.

The present invention relates to a thermally active delayed fluorescent compound having a specific structure as an acceptor, a material for an organic device containing the above compound, a composition for forming a light emitting layer, an organic electroluminescent device containing the compound in the light emitting layer, and an organic electroluminescence device. The present invention relates to an effect transistor or an organic thin film solar cell, and a display device and a lighting device including the organic electroluminescent element.

Conventionally, display devices using electroluminescent elements that emit electroluminescence have been studied in various ways because they can save power and become thinner. Further, organic electroluminescent elements (organic EL elements) made of organic materials have been made lighter. It has been actively studied because it is easy to increase the size. In particular, regarding the development of organic materials having light emitting characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transporting ability such as holes and electrons, high molecular compounds and low molecular compounds are used. Regardless, it has been actively studied so far.

The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers containing an organic compound, which are arranged between the pair of electrodes. Layers containing organic compounds include light emitting layers and charge transport / injection layers that transport or inject charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

There are mainly two light emitting mechanisms of the organic EL element: fluorescence light emission using light emission from the excited singlet state and phosphorescent light emission using light emission from the excited triplet state. Common fluorescent materials have low exciton utilization efficiency of about 25%, triplet-triplet fusion (TTF: Triplet-Triplet Fusion, or triplet-triplet annihilation, TTA: Triplet-Triplet Annihilation). ) Is also used, and the exciton utilization efficiency is 62.5%. On the other hand, the phosphorescent material may reach 100% exciton utilization efficiency, but it is difficult to realize deep blue light emission, and in addition, there is a problem that the color purity is low because the emission spectrum is wide.

As the compound used for the organic EL device, for example, the compounds described in Patent Document 1 or Non-Patent Documents 1 to 4 are known.

Japanese Patent No. 5669163

Therefore, Professor Chihaya Adachi of Kyushu University proposed a donor-acceptor type (DA type) thermoactive delayed fluorescence (TADF: Thermally Assisting Delayed Fluorescence) mechanism (see Non-Patent Document 1). The DA type TADF compound has a structure in which the donor structure and the acceptor structure are bonded directly or via a π or σ bond, and absorbs heat energy to change from an excited triplet state to an excited singlet state. It is a compound that can cause inverse intersystem crossing, deactivate by radiation from its excited singlet state, and emit fluorescence (delayed fluorescence). By using such a TADF compound, the energy of triplet excitons can also be effectively utilized for fluorescence emission, so that the exciton utilization efficiency of emission reaches 100%. A characteristic of the DA type TADF compound is that it gives a wide emission spectrum with low color purity due to its structure, but the rate of inverse intersystem crossing is extremely high.

In addition, Professor Hatakeyama of Kwansei Gakuin University has proposed a molecular design of a TADF-active compound using the multiple resonance effect (Non-Patent Document 3 and Patent Document 1). In molecular design using the multiple resonance effect, boron (electron attracting property) and nitrogen (electron donating property) are bonded to each other at the o-position. As a result, the HOMO and LUMO formed by each are strengthened and localized on the atom, so that the separation of HOMO and LUMO and the TADF property are obtained. The robust planar structure formed provides an emission spectrum with high color purity with low Stokes shift of absorption and emission peaks. On the other hand, the speed of the inverse intersystem crossing is inferior to that of the DA type TADF compound.

In the DA type TADF compound, an emission spectrum with high color purity can be realized by utilizing a DA structure in which structural changes and rotations are restricted (Non-Patent Document 2). Based on the same idea, compounds having a narrow half-value width at half maximum have been proposed using an acceptor structure having a boron atom (Patent Documents B, Non-Patent Documents C and D), and the half-value width at half maximum has been improved. On the other hand, even if a similar donor structure is used, a narrow half-value width at half maximum, a fast intersystem crossing speed, and blue light emission cannot be obtained (Non-Patent Document 4).

As mentioned above, it was difficult to realize all of the narrow half-value width at half maximum, high TADF activity, and blue light emission, and there was room for improvement in the optimization of the partial structure for these realizations.

An object of the present invention is to provide a novel compound as a material used for an organic device such as an organic EL element.

As a result of diligent studies to solve the above problems, the present inventors have found a new combination of an acceptor structure and a donor structure. The present invention has been proposed based on such findings, and has the following configuration as a specific example.

[1] A compound having at least one structure represented by the following formula (i);

In formula (i),
Rings A, B and C each independently represent an aromatic ring structure.
At least one ring member atom in at least one of the A ring, the B ring and the C ring is bonded to the partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , respectively.
In the partial structure (D), Q is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the wavy line indicates the bond position.
A ring member atoms contained in the ring member atoms and C ring contained in the B ring is bridged by X ^3, a portion of the part and C rings of the ring B and may form a 6-membered ring containing Y, X ³ is any one of>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ .
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Diarylboryl (two aryls may be attached via a single bond or a linking group), a substituent that is cyano or halogen, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
The R'in the above-mentioned Si-R',>N-R',> C (-R') ₂ and> Si (-R') ₂ can be independently hydrogen, aryl, heteroaryl, alkyl or Cycloalkyl,
In the A ring, B ring and C ring in the formula (i), the structure bonded to the ring member atom not bonded to the partial structure (D), X ¹ , X ² , or Y, and R ²¹ in the partial structure (D). ~ R ²⁸ is not all hydrogen,
At least one hydrogen in the compound having at least one structure represented by the formula (i) may be substituted with cyano, halogen, deuterium, or partial structure (B).

(In the partial structure (B), R ⁴⁰ and R ⁴¹ are each independently alkyl and may be bonded to each other, and the total carbon number of R ⁴⁰ and R ⁴¹ is 2 to 10, and the wavy line portion is It is a binding site with other structures.)

[2] The compound according to [1] represented by the following formula (1);

In equation (1),
At least one of R ¹ to R ¹¹ is a partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , respectively.
R ¹ to R ¹¹ which are not partial structures (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy. , Or diarylboryl (two aryls may be attached via a single bond or a linking group), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
R ⁷ and R ⁸ may be crosslinked at> X ³ to form a 6-membered ring containing part of the b ring, part of the c ring and Y, where X ³ is>O,>S,> N-. R',> C (-R') ₂ or> Si (-R') ₂
The R'in Si-R',>N-R',> C (-R') ₂ and> Si (-R') ₂ are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. The _two R'of each of the> C (-R') ₂ and> Si (-R') ₂ may be connected.
R ¹ to R ¹¹ which are not the partial structure (D) in the formula (1) and R ²¹ to R ²⁸ in the partial structure (D) are not all hydrogen.
At least one hydrogen in the compound represented by the formula (1) may be substituted with halogen or deuterium.

[3] In equation (1)
At least one selected from the group consisting of R ¹ and R ³ is a partial structure (D).
R ¹ to R ¹¹ which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryls), diheteroarylaminos (where heteroaryls are heteroaryls with 2-12 carbon atoms), aryl heteroarylaminos (where aryls are aryls with 6-12 carbon atoms and heteroaryls have 2 carbon atoms). It is a substituent that is an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms (which is a heteroaryl of to 12), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these may be formed and is substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
R ⁷ and R ⁸ may be crosslinked with> X ³
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 12 carbon atoms). Aryl), diheteroarylamino (where heteroaryl is a heteroaryl having 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is an aryl having 6 to 12 carbon atoms and heteroaryl is an aryl having 2 to 12 carbon atoms). Heteroaryl), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cyano or halogen substituents, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May have been
R'is described in [2], which is independently an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms. Compound.

[4] In equation (1)
R ² is the partial structure (D).
R ¹ to R ¹¹ which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl substituent that is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms without substitution, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
Moiety Q is in the structure (D)> C (-R ' ) 2, a partial structure> in _{(D) C (-R')} R in ₂ 'methyl and the partial structure (D) ^{^R} 21 ^~ ^R ²⁸ in When is hydrogen, R ⁶ and R ⁹ in the formula (1) are independently partial structures (D), hydrogen, or aryls having 6 to 30 carbon atoms, heteroaryls having 2 to 30 carbon atoms, respectively. Diarylamino (where aryl is aryl with 6-12 carbon atoms), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms), Heteroaryl is a substituent that is an alkyl having 2 to 12 carbon atoms, an alkyl having 1 to 3 carbon atoms without substitution, or a cycloalkyl having 3 to 20 carbon atoms. Among these substituents, adjacent substitution groups are used. The groups may be bonded to each other to form a ring structure, and at least one hydrogen in these substituents is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl or carbon having 1 to 12 carbon atoms. It may be substituted with the number 3 to 20 cycloalkyl.
The compound according to [2].

[5] In equation (1)
At least one selected from the group consisting of R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ is a partial structure (D).
R ¹ to R ¹¹ which are not partial structures (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms, and among these substituents, adjacent substituents may be bonded to each other to form a ring structure. At least one hydrogen in these may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.
R ⁷ and R ⁸ may be crosslinked with> X ³
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 12 carbon atoms). Aryl), diheteroarylamino (where heteroaryl is a heteroaryl having 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is an aryl having 6 to 12 carbon atoms, and heteroaryl is an aryl having 2 to 12 carbon atoms). (12 heteroaryl), alkyl with 1-12 carbon atoms, cycloalkyl with 3-20 carbon atoms, cyano or halogen substituents, of which adjacent substituents are attached to each other. A ring structure may be formed, and at least one hydrogen in these substituents is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms, or an alkyl having 3 to 20 carbon atoms. May be substituted with cycloalkyl
R'is independently an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms.
The compound according to [2].

[6] In equation (1), X ¹ and X ² are independently>O,>S,> C (-R') ₂ or> Si (-R') ₂ , respectively, [2]. The compound according to any one of [5].
[7] The compound according to any one of [2] to [6], wherein both X ¹ and X ² are> O in the formula (1).
[8] The compound according to any one of [2] to [7], wherein Y is B in the formula (1).
[9] The compound according to any one of [2] to [7], wherein Y is P = O or P = S in the formula (1).
[10] The compound according to any one of [2] to [7], wherein Y is Si—R'in formula (1).
[11] The compound according to any one of [2] to [10], wherein R ⁷ and R ⁸ do not crosslink and form a ring in the formula (1).
[12] The compound according to any one of [2] to [10], wherein R ⁷ and R ⁸ are crosslinked at> X ³ to form a ring in the formula (1).
[13] The compound according to any one of [2] to [12], which has one partial structure (D) in the formula (1).
[14] The compound according to any one of [1] to [13], wherein Q in the partial structure (D) is> O or> S.
[15] The compound according to any one of [1] to [13], wherein Q in the partial structure (D) is> C (-R) ₂ or> Si (-R) ₂ .

[16] The compound according to [2], which is a compound represented by any of the following formulas.

(In the formula, Me represents methyl and tBu represents t-butyl.)

[17] The compound according to [1] represented by the following formula (ii);

In formula (ii),
Rings a, b, c and d are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted, and two adjacent hydrogens may be substituted. They may be linked by alkyl to form a ring.
Z ¹ and Z ² are independently -CH = or -N =, and the hydrogen at -CH = may be substituted.
X ¹ to X ⁴ are independently O or N-R, and R of the N-R is aryl, heteroaryl or alkyl, respectively.
At least one ring member atom in at least one ring selected from the group consisting of a ring, b ring, c ring, d ring, and a 6-membered ring including Z ¹ and Z ² is bonded to the partial structure (D). And
In the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, and adjacent R ²¹ to R ²⁸ are based on linking groups. It may form a ring,
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the above> C (-R') ₂ and> Si. (-R') The R'of ₂ is an aryl that may be independently linked with hydrogen, alkyl, or R', respectively.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is a single bond, both R ²⁴ and R ²⁸ do not become hydrogen.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X ¹ and X ² do not become O.
The wavy line portion in the partial structure (D) represents the binding site with the structure represented by the formula (ii).
At least one hydrogen in the compound represented by the formula (ii) may be substituted with a halogen, deuterium, or a partial structure (B).

[18] The compound according to [17] represented by the following formula (4);

In formula (4), R ¹ to R ¹⁴ are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Alternatively, it is a substituent that is a diarylboryl (two aryls may be attached via a single bond or a linking group), and at least one hydrogen in these substituents is substituted with aryl, heteroaryl or alkyl. May be
Adjacent two of R ³ to R ¹⁴ may be connected by an alkyl having 2 to 8 carbon atoms to form a ring.
X ¹ to X ⁴ are independently O or N-R, and R of the N-R is an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, and 1 to 20 carbon atoms. Alkyl or cycloalkyl with 3-8 carbon atoms
At least one of R ¹ to R ¹⁴ in the formula (4) is a partial structure (D) represented by the formula (D).
In the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, respectively.
Adjacent R ²¹ to R ²⁸ may form a ring with a linking group.
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the above> C (-R') ₂ and> Si. The R'of (-R') ₂ is an independently hydrogen, an alkyl having 1 to 8 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be linked.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is a single bond, both R ²⁴ and R ²⁸ do not become hydrogen.
However, when the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X ¹ and X ² do not become O.
At least one hydrogen in the compound represented by the formula (4) may be substituted with a halogen, deuterium, or a partial structure (B).

[19] In the formula (4), R ¹ to R ¹⁴ are independently hydrogen or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (where aryl has carbon atoms). 6 to 12 aryl), alkyl with 1 to 12 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, aryloxy with 6 to 12 carbon atoms, or diarylboryl (where aryl is aryl with 6 to 12 carbon atoms) (2) One aryl is a substituent (which may be attached via a single bond or a linking group), and at least one hydrogen in these substituents is an aryl having 6 to 12 carbon atoms or an aryl having 1 to 8 carbon atoms. May be substituted with alkyl
X ¹ to X ⁴ are independently> O or> N-R, and R of> N-R is an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 8 carbon atoms.
In the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms, and 3 to 3 carbon atoms. 20 cycloalkyl, cyano, or halogen, where Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ . The R'of> C (-R') ₂ and> Si (-R') ₂ is independently hydrogen or an alkyl having 1 to 8 carbon atoms.
The compound according to [18], wherein at least one hydrogen in the compound represented by the formula (4) may be substituted with halogen or deuterium.

[20] The compound according to [18] or [19], wherein one or two of R ⁴ , R ⁷ , R ¹⁰ and R ¹³ have a partial structure (D) in the formula (4).
[21] The compound according to any one of [17] to [20], wherein at least one of R ²¹ to R ²⁸ is fluorine in the partial structure (D).

[22] The compound according to any one of [17] to [21], wherein the partial structure (D) is a structure represented by any of the following formulas (D-1) to (D-3);

In formula (D-1), R ⁵⁰ independently represents a hydrogen atom or methyl, and Me is methyl.
In formula (D-2), Q ¹ represents>O,>S,> C (CH ₃ ) ₂ , or> Si (CH ₃ ) ₂ .

[23] The compound according to [18], which is represented by any of the following formulas.

(In the formula, Me represents methyl.)

[24] The compound according to any one of [17] to [23], which comprises a partial structure (B), a chlorine atom, a bromine atom, or an iodine atom in the structure.
[25] The energy level difference between S1 and T1 is 0.1 eV or less, the energy level difference between S1 and T2 is 0.05 eV or less, and S1 is in a locally excited state [17] to [ 24] The compound according to any one of.
[26] The compound according to [1], which is a polymer compound having a repeating unit containing a structure represented by the formula (i).
[27] Triarylamines which may have a substituent or a substituent, fluorene which may have a substituent or a substituent, anthracene which may have a substituent or a substituent, and an unsubstituted or substituent. Tetracene which may have, triazine which may have an unsubstituted or substituent, carbazole which may have an unsubstituted or substituent, tetraphenylsilane which may have an unsubstituted or substituent, unsubstituted Alternatively, it has spirofluorene which may have a substituent, triphenylphosphine which may have an unsubstituted or substituent, dibenzothiophene which may have an unsubstituted or substituent, and an unsubstituted or substituent. 26. The compound according to [26], wherein the structure derived from at least one selected from the group consisting of dibenzofurene may be contained in the repeating unit, or in a repeating unit different from the repeating unit.
[28] A material for an organic device containing the compound according to any one of [1] to [27].
[29] The material for an organic device according to [28], which is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.
[30] The material for an organic device according to [29], which is a material for a light emitting layer for an organic electroluminescent element.
[31] An organic electroluminescent device, an organic field effect transistor, or an organic thin-film solar cell containing the compound according to any one of [1] to [27].
[32] An organic electroluminescent device comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and containing the light emitting layer material according to [30].

[33] The light emitting layer contains at least one compound represented by the following formula (H1), formula (H2), formula (H3), formula (H4), or formula (H5), or the following ( [32], which contains at least one polymer compound having a structure derived from a compound represented by H1), formula (H2), formula (H3), formula (H4), or formula (H5) as a repeating unit. The organic electroluminescent element described;

In the formula (H1), L ¹ is an arylene having 6 to 24 carbon atoms.
In formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms, respectively.
At least one hydrogen in the compound represented by each of the above formulas may be substituted with alkyl, cyano, halogen or deuterium having 1 to 6 carbon atoms.
In formula (H3), J is>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ .
Y is a single bond,>O,>S,> C (-R') ₂ , or> Si (-R') ₂ .
Z is CH, CR'or N,
In formula (H4), Z is CH, CR'or N,
The R'in>N-R',> C (-R') ₂ ,> Si (-R') ₂ and C-R'are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. Yes,
In formula (H5),
R ¹ to R ¹¹ are substituents that are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, and at least one of these substituents. The two hydrogens may be further substituted with aryl, heteroaryl, diarylamino or alkyl,
Adjacent groups of R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, in which at least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino or alkyl. Often,
At least one hydrogen in the compound represented by the formula (H5) may be independently substituted with a halogen or deuterium.

[34] The organic electroluminescent device according to [32] or [33], which contains at least one compound represented by any of the following formulas (AD1), (AD2) and (AD3);

In formulas (AD1), (AD2) and (AD3),
M is at least one of single bond, -O-,> N-Ar and> CAR ₂ independently of each other.
Each of J is independently an arylene having 6 to 18 carbon atoms, and the arylene may be replaced with phenyl, an alkyl having 1 to 6 carbon atoms, and a cycloalkyl having 3 to 12 carbon atoms.
Q is = C (-H)-or = N-, respectively.
Ar is independently hydrogen, an aryl having 6 to 18 carbon atoms, a heteroaryl having 6 to 18 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms, and the aryl and hetero At least one hydrogen in the aryl may be replaced with phenyl, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms.
m is 1 or 2
n is an integer from 2 to (6-m),
At least one hydrogen in the compound represented by each of the above formulas may be substituted with halogen or deuterium.

[35] A composition for forming a light emitting layer, which comprises at least one of the compounds according to any one of [1] to [27] and a solvent.
[36] The composition for forming a light emitting layer according to [35], which comprises an organic solvent having a boiling point of 150 ° C. or higher as the solvent.
[37] The above-mentioned [35] or [36], wherein the solvent is a mixed solvent containing a good solvent and a poor solvent for at least one of the compounds, and the boiling point of the good solvent is lower than the boiling point of the poor solvent. A composition for forming a light emitting layer.

[38] Contains at least one compound represented by the formula (H1), the formula (H2), the formula (H3), the formula (H4), or the formula (H5), or the formula (H1), the formula (H2). ), Formula (H3), formula (H4), or at least one polymer compound having at least one of the structures derived from the compound represented by the formula (H5) as a repeating unit, [35] to [37]. ] The composition for forming a light emitting layer according to any one of

In the formula (H1), L ¹ is an arylene having 6 to 24 carbon atoms.
In formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms, respectively.
At least one hydrogen in the compound represented by each of the above formulas may be substituted with alkyl, cyano, halogen or deuterium having 1 to 6 carbon atoms.
In formula (H3), J is>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ .
Y is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ .
Z is CH, CR'or N,
In formula (H4), Z is CH, CR'or N,
The R'in>N-R',> C (-R') ₂ ,> Si (-R') ₂ and C-R'are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. Yes,
In formula (H5),
R ¹ to R ¹¹ are substituents that are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, and at least one of these substituents. The two hydrogens may be further substituted with aryl, heteroaryl, diarylamino or alkyl,
Adjacent groups of R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, in which at least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino or alkyl. Often,
At least one hydrogen in the compound represented by the formula (H1), the formula (H2), the formula (H3), the formula (H4), or the formula (H5) is independently substituted with a halogen or a deuterium. You may.

[39] It has a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and formed from the light emitting layer forming composition according to any one of [35] to [38]. , Organic electroluminescent device.
[40] It has at least one layer selected from the group consisting of an electron transport layer and an electron injection layer arranged between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer. Is a group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol metal complexes. The organic electric field light emitting element according to any one of [32] to [34], and [39], which contains at least one selected from.
[41] At least one of the electron transport layer and the electron injection layer is an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth. It further contains at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. , [40]. The organic electric field light emitting element.
[42] A display device or a lighting device including the organic electroluminescent element according to any one of [32] to [34] and [39] to [41].

According to the present invention, a novel compound is provided as a material used for an organic device such as an organic EL element. The compound of the present invention is useful as a material for an organic device that can be used in the manufacture of an organic electroluminescent device, an organic field effect transistor, or an organic device such as an organic thin-film solar cell.

It is a schematic sectional drawing which shows the organic EL element which concerns on this embodiment. It is a figure which shows the plot of the partial HOMO and delayed fluorescence lifetime of a substituent.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present specification, "hydrogen" in the description of the structural formula means "hydrogen atom (H)".
In the present specification, the structure derived from a specific compound when describing a polymer compound is a structure that includes most of the structure of the compound and can be a repeating unit of the polymer compound. For example, a structural unit derived from the monomer in a polymer compound obtained by polymerizing a monomer having a structure in which any one hydrogen of the compound is substituted with a polymerizable group, or two or more hydrogens of the compound. Examples thereof include structural units derived from the reactive compound when the reactive compounds independently substituted with the reactive groups are bonded to each other to form a polymer compound.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

In the present specification, the "thermally active delayed phosphor" (TADF compound) absorbs thermal energy to cause an intersystem crossing from an excited triplet state to an excited singlet state, and radiates from the excited singlet state. It means a compound that can be deactivated and emit delayed fluorescence. Here, the "thermally active delayed phosphor" also includes those that undergo a higher-order triplet in the excitation process from the excited triplet state to the excited singlet state. The luminescence mechanism that emits fluorescence via higher triplets is called the FvHT (Fluorescence via Higher Triplet) mechanism. For example, a paper by Durham University Monkman et al. (NATURE COMMUNICATIONS, 7:13680, DOI: 10.1038) / ncomms13680), National Institute of Advanced Industrial Science and Technology Hosogai et al. (Hosokai et al., Sci. Adv. 2017; 3: e1603282), Kyoto University Sato et al. (Scientific Reports, 7: 4820, DOI: 10.1038 / s41598- 017-05007-7) and a presentation by Sato et al. Of Kyoto University (98th Annual Meeting of the Chemical Society of Japan, presentation number: 2I4-15, mechanism of high-efficiency luminescence in organic EL using DABNA as a luminescent molecule, Kyoto It is described in (Graduate School of Engineering, Durham University). In the present invention, when the fluorescence lifetime of a sample containing the target compound is measured at 300 K, it is determined that the target compound is a "thermoactive delayed phosphor" when a slow fluorescence component is observed. Here, the "slow fluorescence component" refers to a substance having a fluorescence lifetime of 0.1 μsec or more. On the other hand, the fluorescence emitted from the excited singlet state generated by the direct transition from the basis singlet state usually has a fluorescence lifetime of 0.1 nsec or less. In the following description, fluorescence having a lifetime of 0.1 nsec or less is referred to as a "fast fluorescence component". The fluorescence emitted by the "thermoactive delayed phosphor" used in the present invention may contain a fast fluorescent component as well as a slow fluorescent component.
The fluorescence lifetime can be measured using, for example, a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C11367-01).

In this specification, unless otherwise indicated, "E _S1" indicates the excited singlet energy level obtained from the intersection between the tangent line and a base line passing through the inflection point of the short wavelength side of the fluorescence spectrum in 77K, " E _T1 "indicates the excited triplet energy level obtained from the intersection between the tangent line and a base line passing through the inflection point of the short wavelength side of the phosphorescence spectrum in 77K, a" Delta] E _ST "is E _T1 from the E _S1 subtracting the energy difference, _ie, a value calculated by E S1 _{-E T1.} Delta] E _ST is less than 0.20 eV, preferably not more than 0.15 eV, more preferably less 0.10 eV.

"Fluorescent substance" means a compound that can radiate fluorescence by being radiated from the excited singlet state. The phosphor may be a normal phosphor in which only a fast fluorescence component is observed when the fluorescence lifetime is measured at 300 K, or a delayed fluorescence in which both a fast fluorescence component and a slow fluorescence component are observed. There may be. The fluorescence singlet energy level obtained from the shoulder on the short wavelength side of the peak of the fluorescence spectrum of the phosphor is lower than that of the host compound as the first component and the thermally active delayed phosphor as the second component. preferable.

In the present invention, the "emitter" refers to a compound that emits light that is contained in a light emitting layer and is finally taken out of the device in an organic EL device, and even a plurality of compounds have different emission wavelengths. It doesn't matter. In particular, the emitter used in the "TAF element" (TADF Assisting Fluorescence element) described later is called an "emitting dopant". The compounds of the present invention can be used as emitters and can function as emerging dopants or "assisting dopants", especially in TAF devices. The "heat-activated delayed phosphor" can function as an assisting dopant that assists in the emission of the phosphor. In particular, in the TAF element, the assisting dopant reverse-exchanges the electrons and holes received from the host from the excited triplet energy to the excited singlet energy on the assisting dopant following recombination to the emerging dopant. Hand over energy. In the following description, an organic electroluminescent device that uses a thermally active delayed phosphor as an assisting dopant may be referred to as a “TAF device”. In the TAF element, the excited triplet energy is converted into the excited singlet energy by the inverse intersystem crossing in the thermoactive delayed phosphor, so that the excited singlet energy is efficiently supplied to the phosphor to assist the light emission. Can be done. As a result, high luminous efficiency can be obtained.

The host, assisting dopant, and emerging dopant used in the present invention preferably have energy levels that satisfy at least one of the following formulas (a) to (c), and more preferably satisfy all the conditions.
｜ Ip (H) ｜ ≧ ｜ Ip (AD) ｜・・・ Equation (a)
In the formula (a), Ip (H) represents the ionization potential of the host compound, and Ip (AD) represents the ionization potential of the assisting dopant.
｜ Eg (AD) ｜ ≧ ｜ Eg (ED) ｜・・・ Equation (b)
In the formula (b), Eg (AD) represents the energy difference between the ionization potential and the electron affinity of the assisting dopant, and Eg (ED) represents the energy difference between the ionization potential and the electron affinity of the emittering dopant.
ΔEST (H) ≧ ΔEST (AD) ・・・ Equation (c)
In formula (c), ΔEST (H) represents the energy difference between the excited single-term energy level and the excited triple-term energy level of the host compound, and ΔEST (AD) is the excited single-term energy level of the assisting dopant. Represents the energy difference between the excited triplet energy level and.

On the other hand, the emitting dopant preferably has an emission peak in which the full width at half maximum FWHM is 80 nm or less in the range of 440 to 590 nm of the fluorescence spectrum. For applications of the blue light emitting device, 450 to 475 nm is more preferable, and 455 to 465 nm is further preferable. For applications of the green light emitting device, 490 to 590 nm is more preferable, and 510 to 550 nm is further preferable. When the full width at half maximum FWHM of the emission peak is 35 nm or less, it means that the color purity of the emission is high. Therefore, by using such a phosphor, an organic light emitting device having a good color can be realized.

In the present specification, the ionization potential (Ip) means the ionization potential (Ip) by photoelectron yield spectroscopy (Photoelectron Yield Spectroscopy), and the energy gap (Eg) is the longest wavelength side of the spectrum obtained by ultraviolet visible absorption spectroscopy. It means the optical band gap obtained from the intersection of the tangent line of the absorption peak and the baseline, and the electron affinity (Ea) means the electron affinity obtained by reducing Eg from Ip.

In the present specification, as a measurement sample for measuring each energy level, when the target compound is a host compound or an assisting dopant, a single film (Neat film, thickness) of the target compound formed on the glass substrate is used. When the target compound is an emitting dopant using (50 nm), an inert polymer film (for example, a polymethylmethacrylate film. In addition, polystyrene, etc.) formed on a glass substrate and dispersed with the target compound is used. Cytop, Zeonex, etc. may be used. Thickness: 10 μm, concentration of target compound: 1% by mass) is used. The film thickness of the polymethylmethacrylate film in which the target compound is dispersed may be a film thickness that is sufficient for measuring the absorption spectrum, fluorescence spectrum, and phosphorescence spectrum. If the intensity is weak, the film thickness is thick and the intensity is high. If it is strong, it should be thinned. For the excitation light, the wavelength of the absorption peak obtained in the absorption spectrum is used, and among the emission peaks appearing in the fluorescence spectrum or the phosphorescence spectrum, the blue emission is in the range of 400 to 500 nm, and the green emission is in the range of 400 to 500 nm. Is to be obtained for each energy level using the data obtained from the emission peaks appearing in the range of 480 to 600 nm and in the case of red in the range of 580 to 700 nm. Further, when the absorption peak and the emission peak are close to each other and the excitation light is mixed in the emission peak, the absorption peak or the absorption shoulder on the shorter wavelength side may be used.
[1] Fluorescence spectra excited singlet energy level determined from the intersection between the peak short wavelength side of the tangent and baseline E _S1
The measurement sample containing the target compound is irradiated with excitation light at 77K, and the fluorescence spectrum is observed. For the emission peak appearing in the fluorescence spectrum, draw a tangent line passing through the inflection point on the short wavelength side, and from the wavelength ( _BSh ) [nm] of the intersection of the tangent line and the baseline, use the following formula. The excited single-term energy level _ES1 is calculated.
E _S1 [eV] = 1240 / B _Sh
[2] excited triplet determined from the intersection between the tangent line and the base line of the peak short wavelength side of the phosphorescence spectrum energy level E _T1
The measurement sample containing the target compound is irradiated with excitation light at 77K, and the phosphorescence spectrum is observed. For the emission peak appearing in the phosphorescence spectrum, draw a tangent line passing through the turning point on the short wavelength side, and use the following equation from the wavelength ( _CSh ) [nm] of the intersection of the tangent line and the baseline. The excited triplet energy level _ET1 is calculated.
_ET1 [eV] = 1240 / C _Sh

Here, the DA (donor-acceptor) type TADF material and the MRE (Multi Resonance Effect) type compound have different emission widths of fluorescence and phosphorescence spectra due to the robustness of the molecule, so that the maximum emission wavelength is different. Even if they are the same, it is considered that the DA type TADF compound has a wider range of energy possessed by the molecule than the MRE type compound molecule. Since it is necessary to accurately estimate the energy transfer between each component and design the configuration of the TAF element, the excited singlet energy level and the excited triplet energy level are estimated from the short wavelength side of the spectrum.

(5) Intersystem crossing velocity The intersystem crossing velocity indicates the velocity of the intersystem crossing from the excited triplet to the excited singlet. The inverse intersystem crossing velocity of a thermoactive delayed phosphor shall be calculated by transient fluorescence spectroscopy using the method described in Nat. Commun. 2015, 6, 8476. Or Organic Electronics 2013, 14, 2721-2726. can be, specifically, the reverse intersystem crossing rate of heat activated delayed fluorescent substance is a ¹⁰ 5 ^{s -1} or more, ^preferably, 10 ^{6 s -1} or more.

(6) Emission velocity The emission velocity indicates the rate of transition from the excited singlet to the ground state via fluorescence emission without going through the TADF process. The emission rate of the thermoactive delayed fluorophore can be calculated using the method described in Nat. Commun. 2015, 6, 8476. Or Organic Electronics 2013, 14, 2721-2726, as well as the intersystem crossing rate. Specifically, the emission rate of the thermally active delayed phosphor is 10 ⁷ s ^-1 or more, and more preferably 10 ⁸ s ^-1 or more.
Hereinafter, the compound of the present invention, an organic electroluminescent device using the compound, and the like will be described.

In the present specification, HOMO / LUMO, energy gap, (minimum) excited singlet energy having prefixes such as "partial" / "localized" / "charge transfer transition". The compounds of the present invention will be described using terms such as, and (lowest / higher order) excited triplet energies. Some of these are values obtained by molecular orbital calculation, not values obtained optically or electrochemically by measuring the compound of the present invention, and have a correlation with actual measurement (or with actual measurement). It can be inferred that there is a correlation), but the numbers may not match. For ease of design and verification of the molecular structure, it is decomposed into a donor structure and an acceptor structure, and calculations, measurements, and explanations are performed. Therefore, when describing the partial structure of the acceptor or donor, only the acceptor structure or only the donor structure may be considered.

1. 1. Compound The compound of the present invention is a compound having at least one structure represented by the following formula (i).
The compound of the present invention has a structure represented by the formula (i) as an acceptor structure (A) excluding the partial structure (D), and a partial structure (D) as a donor structure. I can say.
In a series of papers (Nature 492, 234-238, Science Advances, 2017: 3, e1603282, Science Advances 2018: 4, eaao6910) by Adachi et al., Kyushu University, it is necessary for thermoactive delayed fluorescent compounds with high TADF properties. Features have been clarified. The compounds of the present invention have the characteristics described in these papers: HOMO localized on the donor, LUMO localized on the acceptor, and spin inversion via small ΔE _S1T1 and localized transitions. It is considered to have the characteristic of showing the process.

In formula (i),
Rings A, B and C each independently represent an aromatic ring structure.
At least one ring member atom in at least one of the A ring, the B ring and the C ring is bonded to the partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , respectively.
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the wavy line indicates the bond position.
A ring member atoms contained in the ring member atoms and C ring contained in the B ring is bridged by X ^3, a portion of the part and C rings of the ring B and may form a 6-membered ring containing Y, X ³ is any one of>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ .
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Diarylboryl (two aryls may be attached via a single bond or a linking group), a substituent that is cyano or halogen, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
The R'in the Si-R',>N-R',> C (-R') ₂ and> Si (-R') ₂ are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. Yes,
In the A ring, B ring and C ring in the formula (i), the structure bonded to the ring member atom not bonded to the partial structure (D), X ¹ , X ² , or Y, and R ²¹ in the partial structure (D). ~ R ²⁸ is not all hydrogen,
At least one hydrogen in the compound having at least one structure represented by the formula (i) may be substituted with cyano, halogen or deuterium.

The compound of the present invention is a compound having a robust cyclic structure having a hetero element at least in the center or a structure utilizing a multiple resonance effect as an acceptor structure (A) and a structure having nitrogen as a donor structure (D). It is a DA type thermoactive delayed phosphor or a multiple resonance effect delayed phosphor. In the compound of the present invention, high TADF activity can be obtained by bringing the higher-order excited triplet energy level and the excited singlet energy level closer to each other by appropriately selecting the donor (D) and the acceptor (A). More specifically, a compound having high luminous efficiency, fast delayed fluorescence lifetime, blue emission and short emission half width is preferable. It is presumed that this compound is contained in the light emitting layer as an emitter or an assisting dopant in an organic EL device, for example, and can realize high external quantum efficiency and long life.

The first aspect of the compound of the present invention is a compound having a structure represented by the formula (i) as a monomer (preferably a monomer having a structure represented by the formula (1)). It is a compound that suppresses the rotation of a strong donor structure and acceptor structure, and has both blue CT emission having a narrow half-value width and extremely high TADF properties.
A second aspect of the compound of the present invention is a compound that is a multimer of the structure represented by the formula (i) (preferably a compound represented by the formula (4)), which has an acceptor structure. It is a compound that has both an extremely narrow half-value width at half maximum emission and high TADF properties using the LE state (locally excited state) inside. The LE state means S1 when the S0-S1 transition, which is a LE-like transition, is shown. The "LE transition" represents a local energy transition between HOMO-LUMOs that are present on the same partial structure within the molecule. In general, the emission obtained by the "LE transition" is a spectrum having one or more emission peaks having a narrow half width or overlapping them, and a clear vibration peak is often seen. On the other hand, the CT state (charge transfer state) means S1 at the time of the S0-S1 transition, which is a CT-like transition. "CT transition" represents an energy transition between HOMO-LUMOs that are spatially separated on different partial structures within the molecule. In general, the emission obtained by the "CT transition" is a spectrum having an emission peak with a wide half-value width, and no clear vibration peak is observed.

The present invention includes two aspects, in which case it is important to control the higher order excited triplet energy (Tn). In other words, by bringing the HOMO-n (partial structure D) level closer to the HOMO (main skeleton) level and bringing Sn and Tn closer, the up-conversion from the excited triplet to the excited singlet by TADF can be accelerated. it can. More specifically, for the first, by accelerating the up-conversion of T1 (CT) → Tn (LE) → S1 (CT), the other is T1 (LE) → Tn (CT) → S1 (LE). ) Accelerate up-conversion. Specifically, S1-T1 is preferably 0.20 eV or less, S1-T2 (or S1-T3) is preferably 0.20 eV or less, S1-T1 is 0.15 eV or less, and S1-T2 (or S1-T3) is. More preferably 0.10 eV or less. It is more preferable that S1-T1 is 0.1 eV or less and S1-T2 (or S1-T3) is 0.05 eV or less.
In particular, the energy level difference between S1 and T1 (S1-T1) is 0.1 eV or less, the energy level difference between S1 and T2 (S1-T2) is 0.05 eV or less, and S1 is in a locally excited state. Is preferable.

1-1. The acceptor structure excluding the partial structure (D) in the structure represented by the acceptor structural formula (i) has a large partial energy gap ( _Eg (A)) and a high partial minimum triplet excitation energy (E). _{It has T1} (A)). This is because the 6-membered ring containing the hetero element has a low aromatic attribute, so that the decrease in the partial energy gap due to the expansion of the conjugated system is suppressed, and the triplet excited state (T1) is due to the electronic perturbation of the hetero element. ) Is due to the localization of partial SOMO1 and SOMO2. The acceptor structure is preferable as an acceptor structure of a heat-activated delayed fluorescent material because it has a high partial minimum excited triplet energy.

In formula (i), the A ring, B ring and C ring each independently represent an aromatic ring structure. The aromatic ring structure is a structure including an aromatic ring in which the ring member atoms constituting the aromatic ring in the formula (i) are directly bonded to Y and X ¹ and / or X ² . Further, the formula (i) includes at least one aromatic ring structure in which a ring member atom is bonded to the partial structure (D). The aromatic ring structure is preferably an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, and more preferably an aromatic hydrocarbon ring structure.
Further, the A ring, the B ring and the C ring are each independently preferably having a 5-membered ring or a 6-membered ring aromatic ring structure, and more preferably a 6-membered ring aromatic ring structure.
When at least one of the A ring, the B ring and the C ring has an aromatic hydrocarbon ring structure, a benzene ring structure is preferable as the aromatic hydrocarbon ring structure.
When at least one of the A ring, the B ring and the C ring has an aromatic heterocyclic structure, examples of the heteroatom in the aromatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. More specifically, from the viewpoint of enhancing the multiple resonance effect, a pyridine ring structure and a pyrimidine ring structure are preferable, and a pyrimidine ring structure in which N is at the m-position of the carbon to which Y (preferably B) is bonded is more preferable. In other words, when one N in the pyrimidine ring structure is at the 1-position and the other N is at the 3-position, the pyrimidine ring structure that bonds with Y in the formula (i) at the carbon atom at the 5-position is more preferable. Further, in the case of a pyridine ring structure, a pyridine ring in which N is at the m-position of the carbon to which Y (preferably B) is bonded is more preferable. In other words, when N in the pyridine ring is 1-position, a pyridine ring structure that bonds with Y in the formula (i) at the carbon atom at the 3-position or 5-position is more preferable.
The A ring, B ring, and C ring preferably have a benzene ring structure from the viewpoint of ease of synthesis and stability of the compound.
At least one ring member atom in at least one aromatic ring structure of the A ring, B ring and C ring is bonded to the wavy line portion in the partial structure (D).
Here, as a preferred embodiment, a ring member atom in the A ring is bonded to the wavy line portion in the partial structure (D), and a ring member atom in the B ring or the C ring is bonded to the wavy line portion in the partial structure (D). , A mode in which a ring member atom in each of the B ring and the C ring is bonded to a wavy line portion in the partial structure (D), and the like.
In addition, the A ring, the B ring, and the C ring may each independently have a first substituent, which will be described later. Further, at least one hydrogen in the first substituent may be substituted with a second substituent described later.

In formula (i), X ¹ , X ² , Y, partial structure (D), first substituent and second substituent are X ¹ , X ² , Y, partial structure (1) in formula (1) described later. D), synonymous with the first substituent and the second substituent, and the preferred embodiment is also the same.

1-1-1. When the compound having at least one structure represented by the monomer formula (i) is a compound (monomer) having one structure represented by the formula (i), the A ring, the B ring and the C ring In, the ring-membered atoms that are not bonded to the partial structure (D) and that have a bond (carbon, etc.) are independently hydrogen, or aryl, heteroaryl, diarylamino, and dihetero. Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls may be attached via a single bond or a linking group) by binding to a substituent. Adjacent substituents may be bonded to each other to form a ring structure, and at least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

A preferable example of the first aspect of the compound of the present invention is a compound represented by the following formula (1).

In equation (1),
At least one of R ¹ to R ¹¹ is a partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , respectively.
R ¹ to R ¹¹ which are not partial structures (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy. Alternatively, it is a substituent which is a diallylboryl (two aryls may be bonded via a single bond or a linking group), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
R ⁷ and R ⁸ may be crosslinked at> X ³ to form a 6-membered ring containing part of the b ring, part of the c ring and Y, where X ³ is>O,>S,> N-. R',> C (-R') ₂ or> Si (-R') ₂
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Diarylboryl (two aryls may be attached via a single bond or a linking group), a substituent that is cyano or halogen, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
The R'in the Si-R',>N-R',> C (-R') ₂ and> Si (-R') ₂ are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. And
R ¹ to R ¹¹ which are not the partial structure (D) in the formula (1) and R ²¹ to R ²⁸ in the partial structure (D) are not all hydrogen.
At least one hydrogen in the compound represented by the formula (1) may be substituted with halogen or deuterium.

In order to obtain deeper blue luminescence as the compound of the present invention, it is preferable that the partial LUMO in the acceptor is shallow, the partial HOMO is deep, and the partial energy gap is wide, and the specific structure is Y. Is B, P, P = O, P = S or Si-R', preferably B, P = O, P = S or Si-R', and more B, P = O or Si-R'. Preferably, B is even more preferred, where X ¹ and X ² are>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , and>O,>.S,> C (-R') ₂ or> Si (-R') ₂ is preferable,>O,> C (-R') ₂ or> Si (-R') ₂ is more preferable, and both are> O. It is more preferable to have.
Y is preferably B from the standpoints of compound stability, enhanced multiple resonance effects, blue emission of the compound due to wide partial energy gaps, ease of synthesis and high TADF activity.
From the viewpoint of deep blue emission of the compound due to a very wide energy gap and ease of synthesis, Y is preferably P = O or P = S.
From the viewpoint of compound stability and blue emission due to a wide energy gap, Y is preferably Si—R'.

Y may be appropriately used in combination with the donor structure according to the characteristics required for the compound of the present invention. Specific structures include formula (1-B), formula (1-P), formula (1-H), formula (1-T) and formula (1-V). In this case, it is a naphthoanthracene structure having X ¹ , X ² , and Y in the formula (1).

In addition, R ⁷ and R ⁸ may be crosslinked at> X ³ to form a 6-membered ring containing a b ring, a c ring and boron. In this case, it is a triangulene structure having X ¹ , X ² , X ³ and Y. Specific structures include formula (1-BX3), formula (1-PX3), formula (1-HX3), formula (1-TX3) and formula (1-VX3).
However, from the viewpoint of ease of synthesis and high TADF properties, it is preferable that R ⁷ and R ⁸ do not crosslink and do not form a ring.
However, from the standpoint of compound stability and wide energy gap, it is preferred that R ⁷ and R ⁸ crosslink at> X ³ to form a ring.

The naphthoanthracene structure is preferable in terms of ease of partial synthesis and low cohesiveness due to low symmetry. The triangulene structure is preferred in terms of skeletal robustness and strength of intermolecular interaction due to high symmetry. In the present invention, it may be appropriately used in combination with the donor structure.

In X ¹ and X ² , it may be appropriately used in combination with the donor structure according to the characteristics required for the compound of the present invention. Specific structures include formula (1-O2), formula (1-OS), formula (1-OC), formula (1-OI), formula (1-ON), formula (1-S2), and formula. (1-SC), formula (1-SI), formula (1-SN), formula (1-C2), formula (1-CI), formula (1-CN), formula (1-I2), formula ( 1-IN) and formula (1-N2) can be mentioned. From the point of view of the partial energy gap, compounds in which X ¹ and X ² have at least one> O are preferred. From the viewpoint of ease of synthesis, compounds in which both X ¹ and X ² are the same are preferable.

The compounds of the present invention may be Toriangyuren structure has a X ^3. From the viewpoint of partial energy gap and ease of ^synthesis, in X 1, ^{X 2,} and ^{X 3,>O,> S} , a> C (-R _{') 2} or> Si _{(-R') 2} Compounds having one or more, compounds having>N-R'of two or less, and compounds having two or more Xs ^{1 to 3} being the same are preferable, and from the viewpoint of synthesis, X ¹ , X ² , and X more preferably all compounds have the same ^3, from the viewpoint of partial energy ^gap, in X 1, ^{X 2} and ^{X 3,>O,> C} (-R ') 2 or> Si (-R') A compound having one or more of ₂ is more preferable, a compound having one or more of> O is more preferable, and a compound having two or more of> O is even more preferable.

As for the combination of X and Y, in terms of a wide partial energy gap, X ¹ and X ² are>O,>S,> C (-R') ₂ or> Si (-R') ₂ . Compounds that are present and Y is B, P = O or Si-R'are preferred, with X ¹ and X ² or X ¹ , X ² and X ³ being>O,> C (-R') ₂ Or> Si (-R') ₂ and Y is more preferably B, P = O or Si-R', with X ¹ and X ² or X ¹ , X ² and X ³ being Compounds with> O or> C (-R') ₂ and Y being B, P = O or Si-R' are even more preferred, with X ¹ and X ² being> O and> O. Compounds in which Y is B, P = O or Si—R'are even more preferred.
From the viewpoint of compound stability, a compound in which Y is B or Si-R'is preferable, and X ¹ and X ² are>O,>S,> C (-R') ₂ or> Si (-). R') ₂ compounds are more preferred, and X ¹ and X ² are>O,> C (-R') ₂ or> Si (-R') ₂ , more preferably triangular compounds. Is even more preferable.
From the viewpoint of ease of compound synthesis, it is a naphthanthracene type compound, and X ¹ and X ² are>O,>N-R',> C (-R') ₂ or> Si (-R'). ) ₂ is preferred, compounds with the same X ¹ and X ² are more preferred, compounds with both X ¹ and X ² > O are more preferred, and compounds with Y of B or P = O. Is even more preferable.
From the viewpoint of delayed fluorescence lifetime and luminous efficiency of the compound, a naphthanthracene type compound is preferable.

X ¹ and ^{X 2} (and, ^{X 3} if it contains a ^{X 3)} in,> N-R ',> C (-R') 2 or> Si (-R _{') 2} of R' is the number of carbon atoms Aryls of 6 to 20, heteroaryls of 2 to 15 carbons, alkyls of 1 to 20 carbons or cycloalkyls of 3 to 20 carbons, specifically phenyl, biphenyl, fluorenyl, pyridyl, pyrazil, triazil. , Bipyridyl, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, methyl, ethyl, propyl, butyl, cyclohexyl, adamantyl, more preferably phenyl, fluorenyl, methyl. Further, the substituents may form a spiro structure. Further, the _two R's in> C (-R') ₂ or> Si (-R') ₂ may be the same or different.

In Y,> R'of Si—R'is aryl, heteroaryl, alkyl or cycloalkyl, with 6 to 20 carbon atoms, 2 to 15 carbon atoms heteroaryl, 1 to 20 carbon atoms alkyl or It is preferably a cycloalkyl having 3 to 20 carbon atoms. Specifically, phenyl, biphenyl, fluorenyl, pyridyl, pyrazil, triadyl, bipyridyl, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, methyl, ethyl, propyl, butyl, cyclohexyl, or adamantyl are preferred, with phenyl or methyl being more preferred. preferable.

The substitution position of the partial structure (D) in the formula (1) differs depending on the structure of the acceptor structure, but when it is substituted at the p-position of Y, it has a great influence on the partial LUMO in the acceptor structure (A). The naphthoanthracene type structure has lower symmetry than the triangulene type structure, and the influence of the acceptor structure (A) on LUMO can be adjusted by the substitution position, which is preferable. Specifically, the substitution to the naphthoanthracene type structure has a large effect on the substitution on the a ring, and the substitution on the b ring and the c ring has a small effect. That is, for fine adjustment, the partial structure (D) is preferably replaced with R ¹ , R ³ , R ⁴ , R ⁵ , R ⁹ or R ¹¹ . Further, from the viewpoint of the dihedral angle formed by the partial structure (D) and the acceptor structure (A), it is preferable that they are orthogonal to each other. Furthermore, it is preferable that the structural change between the ground state and the excited state is small because an emission spectrum having a narrow half width can be obtained, and the partial structure (D) is replaced with the a ring rather than the b ring and the c ring that cause out-of-plane vibration. Is preferable.

In formula (1), R ¹ to R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls are single-bonded or linked). At least one hydrogen in the aryl, the heteroaryl, and the diarylamino is an aryl, heteroaryl, alkyl or cycloalkyl (or more) (which may be attached via a group) (above, first substituent). , The second substituent) may be substituted.

Examples of the "aryl" (first substituent) include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and 6 to 6 carbon atoms. Aryl of 16 is more preferable, aryl of 6 to 12 carbon atoms is particularly preferable, and aryl of 6 to 10 carbon atoms is most preferable.

Specific examples of the aryl include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-Il, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) Phenantril, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

The above description of "aryl" as the first substituent is described as "aryl" in diarylamino, "aryl" in aryloxy, "aryl" in diarylboryl, and "aryl" as the second substituent. The same can be quoted for "aryl".

Examples of the "heteroaryl" (first substituent) include heteroaryls having 2 to 30 carbon atoms, preferably heteroaryls having 2 to 25 carbon atoms, and more preferably heteroaryls having 2 to 20 carbon atoms. Heteroaryl having 2 to 15 carbon atoms is more preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of heteroaryl include frill, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl Isobenzofuranyl, dibenzofuranyl, benzo [b] thienyl, dibenzothiophenyl, indolyl, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl , Kinoxalinyl, phthalazinyl, naphthyldinyl, prynyl, pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazine, phenazinyl, phenoxatinyl, thianthrenyl, indridinyl and the like.

The above description of "heteroaryl" as the first substituent can also be cited for "heteroaryl" as the second substituent. Further, in the "heteroaryl" as the second substituent, at least one hydrogen in the heteroaryl is an aryl such as phenyl (specific example is the group described above) or an alkyl such as methyl (specific example is a group described later). The substituted group is also included in the heteroaryl as the second substituent. As an example, when the second substituent is carbazolyl, carbazolyl in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl or an alkyl such as methyl is also included in the heteroaryl as the second substituent. ..

The "alkyl" (first substituent) may be either a straight chain or a branched chain, and examples thereof include alkyl having 1 to 24 carbon atoms (branched chain alkyl having 3 to 24 carbon atoms) and having 1 to 24 carbon atoms. An alkyl having 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms (3 carbon atoms) is preferable. (2 to 6 branched chain alkyl) is more preferable, alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) is particularly preferable, and methyl is most preferable.

Specific alkyl examples include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicocil.

The above description of "alkyl" as the first substituent can also be quoted for "alkyl" as the second substituent. The position where the alkyl, which is the second substituent, substitutes for the first substituent is not particularly limited, but is based on the bonding position (1 position) of the first substituent to the a ring, b ring and c ring. The 2nd or 3rd position is preferable, and the 2nd position is more preferable.

"Cycloalkyl" (first substituent) includes cycloalkyl consisting of one ring, cycloalkyl consisting of multiple rings, cycloalkyl containing a double bond that is not conjugated within the ring, and cycloalkyl containing an extracyclic branch. For example, cycloalkyl having 3 to 12 carbon atoms is preferable, cycloalkyl having 5 to 10 carbon atoms is preferable, and cycloalkyl having 6 to 10 carbon atoms is more preferable.

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, decahydronaphthyl, and adamantyl. And so on.

The above description of "cycloalkyl" as the first substituent can also be cited for "cycloalkyl" as the second substituent.

Examples of the "alkoxy" (first substituent) include an alkoxy having 1 to 24 carbon atoms (alkoxy of a branched chain having 3 to 24 carbon atoms) and an alkoxy having 1 to 18 carbon atoms (3 to 18 carbon atoms). (Alkoxy of the branched chain) is preferable, alkoxy having 1 to 12 carbon atoms (alkoxy of the branched chain having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms (alkoxy of the branched chain having 3 to 6 carbon atoms). ) Is more preferable, and an alkoxy having 1 to 4 carbon atoms (alkoxy of a branched chain having 3 to 4 carbon atoms) is particularly preferable.

Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

Further, the details of "aryl" and "heteroaryl" in "diarylamino", "diheteroarylamino", "arylheteroarylamino", "diarylboryl", and "aryloxy" as the first substituent are described. The above-mentioned explanations of "aryl" and "heteroaryl" can be cited.

Even if the two aryls in the "diarylamino" of the first substituent are attached via a single bond or a linking group (eg> C (-R) ₂ ,>O,> S or> N-R) Good. Also, the two aryls in the first substituent "diarylboryl" are attached via a single bond or a linking group (eg> C (-R) ₂ ,>O,> S or> N-R). You may. Here, R of> C (-R) ₂ and> N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (above, the first substituent), and the first is said to be. The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (hereinafter referred to as the second substituent), and specific examples of these groups include aryl and hetero as the first substituent described above. Descriptions of aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy can be cited.

As the alkyl of "dialkylamino" as the first substituent, the above-mentioned explanation of "alkyl" can be cited.

In the formula (1), the adjacent groups of R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, the b ring or the c ring, and in the formed ring. At least one hydrogen may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (above, first substituent), in which at least one hydrogen is aryl, heteroaryl. , Alkyl or cycloalkyl (above, second substituent) may be substituted.

The first substituent (including one substituted with the second substituent) is preferably a group represented by the following structural formula, and more preferably methyl, tertiary alkyl (t-butyl, t). -Amil, t-octyl, etc.), phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xsilyl, 2,6-xsilyl, 2,4,6-mesityl, diphenylamino, di- p-tolylamino, bis (p- (t-butyl) phenyl) amino, and phenoxy, more preferably methyl, t-butyl, t-amyl, t-octyl, phenyl, o-tolyl, 2,6-. Xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, and bis (p- (t-butyl) phenyl) amino. From the viewpoint of ease of synthesis, a larger steric hindrance is preferable for selective synthesis, and specifically, t-butyl, t-amyl, t-octyl, o-tryl, p-trill, 2 , 4-xylyl, 2,5-xsilyl, 2,6-xsilyl, 2,4,6-mesityl, di-p-tolylamino, and bis (p- (t-butyl) phenyl) amino are preferred.

In the following structural formula, "Me" is methyl, "tBu" is t-butyl, "tAm" is t-amyl, "tOct" is t-octyl, and * is the bond position.

1-1-2. Multimer The compound of the present invention may be a multimer having two or more structures represented by the formula (i).
The compound having two or more structures represented by the formula (i) is preferably a compound having both an extremely narrow half-value width at half maximum emission and a high TADF property using the transition of the LE property in the acceptor structure.
Examples of the multimer having two or more structures represented by the formula (i) include the following formulas (i-1), (i-2-1), (i-2-2), and formula (i-3-3). 1), a compound represented by the formula (i-3-2), or the formula (i-3-3) and the like can be mentioned. In a ring shared by a structure represented by two formulas (i) such as the C ring in formula (i-2-1), the two Ys are bonded to each other at the m-position (the shared ring is a benzene ring). In the case of a ring other than the above, it is preferable that the ring member atom to which one Y is bonded is the 1st position in the shared ring, and the ring member atom to which the other Y is bonded is the 3rd position). The same applies to X ¹ and X ² , respectively.

In formula (i-1), rings A to C each independently represent an aromatic ring structure, and at least one ring-membered atom in at least one of the A ring, the B ring, and the C ring is described above. Combined with the wavy line portion in the partial structure (D) represented by the equation (D) of, Y is B, P, P = O, P = S or Si—R', respectively, and X ¹ And X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , and L ¹ is a single bond or n-valent. Represents the organic group of, and n represents an integer of 2 or more.
In formula (i-2-1) or formula (i-2-2), rings A to E each independently represent an aromatic ring structure, and A ring, B ring, C ring, D ring and E ring. At least one ring member atom in at least one ring of the ring is bonded to the wavy line portion in the partial structure (D) represented by the above formula (D), and Y is independently B, P, P = O, P = S or Si-R', and X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si, respectively. (-R') ₂ .
In formula (i-3-1), formula (i-3-2) or formula (i-3-3), A ring, B ring, C ring, D ring, E ring, F ring, G ring, H The ring and the I ring each independently represent an aromatic ring structure, and at least one ring member in at least one of the A ring, the B ring, the C ring, the D ring, the E ring, the F ring, and the G ring. The atom is bonded to the wavy line portion in the partial structure (D) represented by the above formula (D), and Y is independently B, P, P = O, P = S or Si—R'. Yes, X ¹ and X ² are independently>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ .
In formula (i-1), rings A to C, X ¹ , X ² , and Y are independently synonymous with rings A to C, X ¹ , X ² , and Y in formula (i). The same applies to the preferred embodiment.
In the formula (i-1), n represents an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and further preferably 2, 3 or 4. preferable.
In the formula (i-1), L ¹ represents a single bond or an n-valent organic group, preferably an n-valent hydrocarbon group, and an n-valent aliphatic saturated hydrocarbon group or an n-valent aromatic hydrocarbon group. More preferred. Further, when L ¹ is a single bond, n is 2.
In formula (i-2-1) or formula (i-2-2), rings A to E, X ¹ , X ² , and Y are independent of each other, and rings A to C in formula (i). , X ¹ , X ² , and Y, and so do preferred embodiments.
In formula (i-3-1), formula (i-3-2) or formula (i-3-3), rings A to I, X ¹ , X ² , and Y are independently formula (i-3-1). i) It has the same meaning as rings A to C, X ¹ , X ² , and Y in, and the preferred embodiment is also the same.

As the compound of the present invention having a multimer acceptor structure, a compound represented by the following formula (ii) can be mentioned as a preferable example.

In formula (ii),
Rings a, b, c and d are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted, and two adjacent hydrogens may be substituted. They may be linked by alkyl to form a ring.
Z ¹ and Z ² are independently -CH = or -N =, and the hydrogen at -CH = may be substituted.
X ¹ to X ⁴ are independently O or N-R, and R of the N-R is aryl, heteroaryl or alkyl, respectively.
At least one ring member atom in at least one ring selected from the group consisting of a ring, b ring, c ring, d ring, and a 6-membered ring including Z ¹ and Z ² is bonded to the partial structure (D). And
The wavy line portion of the partial structure D is directly bonded to the ring member atom of the a ring to the d ring, or Z ¹ or Z ² .
In the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, and adjacent R ²¹ to R ²⁸ are based on linking groups. It may form a ring,
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the above> C (-R') ₂ and> Si. (-R') The R'of ₂ is an aryl that may be independently linked with hydrogen, alkyl, or R', respectively.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is a single bond, both R ²⁴ and R ²⁸ do not become hydrogen.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X ¹ and X ² do not become O.
The wavy line portion in the partial structure (D) represents the binding site with the structure represented by the formula (ii).
At least one hydrogen in the compound or structure represented by the formula (ii) may be substituted with halogen or deuterium.

In formula (ii), it is preferable that the a ring, the b ring, the c ring and the d ring are independently aryl rings.
When the a ring, b ring, c ring and d ring are heteroaryl rings, examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
It is preferable that the a ring, the b ring, the c ring and the d ring are all benzene rings which may have a substituent.
Further, the a ring, b ring, c ring and d ring may have the above-mentioned first substituent. Further, at least one hydrogen in the first substituent may be substituted by the above-mentioned second substituent.

In formula (ii), Z ¹ and Z ² are independently −CH = or −N =, and −CH = is preferable from the viewpoint of ease of synthesis and stability of the compound. From the viewpoint of the wide energy gap of the compound, −N = is preferable.
The hydrogen in —CH = may be substituted, and examples of the substituent include the partial structure (D) or the above-mentioned first substituent. Further, at least one hydrogen in the first substituent may be substituted by the above-mentioned second substituent.

X ¹ to X ⁴ are independently O or N-R, and from the viewpoint of a narrow full width at half maximum, at least one of X ¹ to X ⁴ is preferably N, and all are N. Is more preferable. In view of the wide energy gap, it is preferable that at least one of X 1 ^~ X ⁴ is O, and more preferably all are O.

Formula (ii) has a partial structure (D) represented by at least one formula (D), and consists of a ring, b ring, c ring, d ring, and a 6-membered ring including Z ¹ and Z ^2. At least one ring member atom in at least one ring selected from the group is bonded to the partial structure (D). The number of the partial structures D in the formula (ii) is preferably 1 to 4, and more preferably 1 to 2. From the viewpoint of the temperature of sublimation purification, the partial structure D is preferably 1. Further, the ring to which the partial structure (D) is bonded is preferably an aromatic ring bonded to N or O, and more preferably an aromatic ring bonded to N. From the viewpoint of good TADF properties, the ring to which the partial structure (D) is bonded is preferably an aromatic ring bonded to one or more N, and an aromatic ring bonded to one or more N and one B. A group ring is more preferable, and an aromatic ring in which two N and one B are bonded is further preferable. From the viewpoint of suppressing cohesiveness, the ring to which the partial structure (D) is bonded is preferably a b ring or a d ring.
The partial structure (D) in the formula (ii) is preferably directly bonded to the ring member atom of the a ring, the b ring, the c ring and the d ring or the carbon atom in Z ¹ or Z ² at a wavy line portion.
Further, in the case of having a plurality of partial structures (D) in the formula (ii), they may have the same structure or different structures.

A preferable example of the compound represented by the formula (ii) is a compound represented by the following formula (4).

In formula (4), R ¹ to R ¹⁴ are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy or It is a substituent that is a diarylboryl (two aryls may be attached via a single bond or a linking group), and at least one hydrogen in these substituents is substituted with aryl, heteroaryl or alkyl. Alternatively, two adjacent two of R ³ to R ¹⁴ may be linked by alkyl having 2 to 8 carbon atoms to form a ring.
X ¹ to X ⁴ are independently O or N-R, and R of the N-R is an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, and 1 to 20 carbon atoms. Alkyl or cycloalkyl with 3-8 carbon atoms
At least one of R ¹ to R ¹⁴ in the formula (4) is a partial structure (D) represented by the formula (D).
In the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, respectively.
Adjacent R ²¹ to R ²⁸ may form a ring with a linking group.
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the above> C (-R') ₂ and> Si. The R'of (-R') ₂ is an independently hydrogen, an alkyl having 1 to 8 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be linked.
However, when the partial structure (D) is bonded only to the a ring and the c ring one by one and Q is a single bond, both R ²⁴ and R ²⁸ do not become hydrogen.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X ¹ and X ² do not become O.
At least one hydrogen in the compound or structure represented by the formula (4) may be substituted with halogen or deuterium.

Wherein ^{^{(4), X 1 ~ X}} 4 have the same meanings as ^X 1 ~ ^{X 4} in the above formula (ii), preferable embodiments thereof are also the same.

In formula (4), R ¹ to R ¹⁴ are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy or It is a substituent which is a diallylboryl (two aryls may be bonded via a single bond or a linking group), and specifically, according to the above description of "first substituent". Further, in the "first substituent", adjacent substituents may be bonded to each other to form a ring structure. Further, at least one hydrogen in the "first substituent" may be substituted with aryl, heteroaryl, or alkyl, and the substituent bonded to the "first substituent" is described in the above "second substituent". According to.

In the formula (4), R ¹ to R ¹⁴ are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (where aryl has 6 to 12 carbon atoms). Aryl), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryloxy or diallylboryl having 6 to 12 carbon atoms (where aryl is an aryl having 6 to 12 carbon atoms). Is preferable. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 8 carbon atoms.
In the formula (4), X ¹ to X ⁴ are independently> O or> NR, and the R of> NR is an aryl having 6 to 12 carbon atoms or 1 to 8 carbon atoms. It is preferably alkyl.
In the formula (4), in the partial structure (D), R ²¹ to R ²⁸ are independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and 1 to 12 carbon atoms, respectively. It is preferably alkyl, cycloalkyl, cyano, or halogen with 3 to 20 carbon atoms, where Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ and> Si. (-R') ₂ and the R'of the> C (-R') ₂ and> Si (-R') ₂ can be independently hydrogen or an alkyl having 1 to 8 carbon atoms. preferable.

From the viewpoint of good TADF activity, it is preferable that one or two of R ⁴ , R ⁷ , R ¹⁰ and R ¹³ have a partial structure (D) in the above formula (4). From the viewpoint of the temperature of sublimation purification, the partial structure (D) is preferably 1. Further, the ring to which the partial structure (D) is bonded is preferably an aromatic ring bonded to N or O, and more preferably an aromatic ring bonded to N. From the viewpoint of good TADF properties, the ring to which the partial structure (D) is bonded is preferably an aromatic ring bonded to one or more N, and an aromatic ring bonded to one or more N and one B. A group ring is more preferable, and an aromatic ring in which two N and one B are bonded is further preferable. From the viewpoint of suppressing cohesiveness, the ring to which the partial structure (D) is bonded is preferably a b ring or a d ring.

When the acceptor structure is a multimer, it is particularly preferable that the acceptor structure is a partial structure represented by the following formula (4-Y2X4-0000).

In the case of a multimer, Y is preferably B, and when it is B, it is represented by a partial structure represented by the following formula (4-B2X4-0000).

X is independently O or N-R, and from the viewpoint of a narrow full width at half maximum, at least one X is preferably N, more preferably three, and all are N. Is more preferable. Further, from the viewpoint of a wide energy gap, it is preferable that at least one X is O, and it is more preferable that all X are O.

Further, as the replacement position of the partial structure (D) in the acceptor structure (A) represented by the formula (4), the p position of B is preferable. From the viewpoint of ease of synthesis, it is preferable that the bond is line-symmetric with respect to the bond between the central benzene ring and Y (here, B), and from the same viewpoint, it is preferable that the molecular weight is small. Specifically, the formula (4-B2X4-04W), the formula (4-B2X4-04W / 07W), the formula (4-B2X4-04W / 09W), the formula (4-B2X4-04W / 07W / 09W) and the formula. (4-B2X4-04W / 07W / 09W / 13W) is preferable, and the formula (4-B2X4-04W), the formula (4-B2X4-04W / 07W) and the formula (4-B2X4-04W / 09W) are more preferable. Further, from the appraisal of the temperature of sublimation purification, the formula (4-B2X4-04W), the formula (4-B2X4-07W), the formula (4-B2X4-04W / 07W) and the formula (4-B2X4-04W / 09W) Preferably, the formula (4-B2X4-04W) and the formula (4-B2X4-07W) are more preferable. On the other hand, from the viewpoint of good TADF property, the partial structure (D) is preferably the p-position of B and the m-position of two Xs, and the formulas (4-B2X4-04W) and (4-B2X4-04W) / 07W), formula (4-B2X4-04W / 09W), formula (4-B2X4-04W / 07W / 09W) and formula (4-B2X4-04W / 07W / 09W / 13W) are preferred, and formula (4-B2X4). −04W / 09W) is more preferable. Here, the partial structure (D) is described by W.

In the acceptor structure (A) represented by the formula (4), substituents other than the partial structure (D) play an important role in adjusting the energy of the acceptor structure (A). When it has only one partial structure (D), the structures described below can be mentioned, and it is preferable to have 1 to 4 substituents other than the partial structure (D), and more preferably 1 to 3 substituents. It is more preferable to have one or two. From the viewpoint of ease of synthesis and temperature of sublimation purification, one is preferable. Here, a substituent other than the partial structure (D) is described by V.

In the acceptor structure (A) represented by the formula (4), substituents other than the partial structure (D) play an important role in adjusting the energy of the acceptor structure (A). As the substituent other than the partial structure (D), the first substituent described later is preferable. More specifically, it suffices if the HOMO of the acceptor structure (A) can be adjusted to be close to the higher-order excitation triplet energy of the donor structure (D), and the partial of the substituent other than the partial structure (D) is partial. From the viewpoint of the energy gap, phenyl which may have an unsubstituted or substituent, pyridine which may have an unsubstituted or substituent, diphenylamine which may have an unsubstituted or substituent, an unsubstituted or substituent Alkyl having 1 to 12 carbon atoms may have, and cycloalkyl having 3 to 12 carbon atoms which may have an unsubstituted or substituent is preferable, and phenyl, tolyl, xsilyl, mesityl, pyridyl, methylpyridyl, and methyl. , Ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl are more preferred. From the viewpoint of ease of synthesis, phenyl, trill, xylyl, mesityl, methyl, butyl and cyclohexyl are preferable.

1-2. Donor structure (partial structure (D))

Q in the partial structure (D) is a single bond,>O,>S,> C (-R') ₂ or> Si (-R') ₂ , and the partial energy gap in the partial structure (D). From the viewpoint,>O,> S or> C (-R') ₂ is preferable, and> O or> S is more preferable. Further, from the viewpoint of the dihedral angle forming a steric hindrance with the acceptor structure (A),>O,>S,> C (-R') ₂ or> Si (-R') ₂ is preferable, and> C ( -R') ₂ or> Si (-R') ₂ is more preferable.

R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. It is a substituent which is diarylboryl (two aryls may be bonded via a single bond or a linking group), cyano or halogen, and specifically, according to the description of the above-mentioned "first substituent". The arylamino may be crosslinked with each other to form a ring structure such as a carbazole ring structure. Further, in the "first substituent", adjacent substituents may be bonded to each other to form a ring structure. Further, at least one hydrogen in the "first substituent" may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and the substituent bonded to the "first substituent" is the "second substituent". Follow the description in.

Further, in the partial structure (D), R'in>N-R',> C (-R') ₂ and> Si (-R') ₂ are independently aryl, heteroaryl, alkyl or cyclo, respectively. It is an alkyl and conforms to the above-mentioned "first substituent".

When Q is a single bond in the partial structure (D), both R ²⁴ and R ²⁸ are preferably not hydrogen, more preferably neither hydrogen, further preferably all alkyl. Is also particularly preferably methyl.

When Q in the partial structure (D) is>O,>S,> C (-R') ₂ or> Si (-R') ₂ , it can be described as follows.

Further, it is preferable that the dihedral angle between the partial structure (D) and the acceptor structure (A) is large from the viewpoint of separating HOMO / LUMO of the compound of the present invention, and it is preferable that R ²⁵ and R ²⁴ have substituents. Further, from the viewpoint of controlling the energy of HOMO, it is preferable to have a substituent at R ²⁷ and / or R ²² . On the other hand, from the viewpoint of synthesis, it is preferable that the molecular weight is small, and hydrogen is preferable for R ²¹ to R ²⁸ . From the above, the structure described below is preferable. In the formulas exemplified herein, Me stands for methyl and tBu stands for tertiary butyl.

Further, the partial structure (D) may be replaced with fluorine. In the partial structure (D), it is preferable that at least one of R ²¹ to R ²⁸ is fluorine.

Among these, the partial structure (D) is preferably a structure represented by any of the following formulas (D-1) to (D-3).

In formula (D-1), R ⁵⁰ independently represents a hydrogen atom or methyl. Also, Me is methyl.
In formula (D-2), Q ¹ represents>O,>S,> C (CH ₃ ) ₂ , or> Si (CH ₃ ) ₂ .

Further, the structural unit represented by the formula (i) or the compound represented by the formula (1) may have only one partial structure (D) or may have two or more partial structures (D). However, from the viewpoint of ease of synthesis, if the B ring and the C ring are not crosslinked (R ⁷ and R ⁸ are not crosslinked) and do not form a ring, the product has two or three partial structures (D). It is preferable that R ⁷ and R ⁸ are crosslinked to form a ring, and it is preferable to have three partial structures (D), and from the viewpoint of the temperature of sublimation purification and the height of Tg, it has only one. Is preferable.

1-3. Characteristics of the compound of the present invention having an acceptor structure (A) and a donor structure (partial structure (D)) The compound of the present invention has at least one partial structure (A) represented by the formula (1). A compound having D), which is a partial HOMO and LUMO of acceptor structure (A) and partial structure (D), HOMO (A), LUMO (A), HOMO (D) and LUMO (D, respectively). ), HOMO (A) is deeper than HOMO (D), and LUMO (A) is deeper than LUMO (D). Also, high for TADF activity, better higher triplet energy _{(E Tn)} needs close to the lowest excited singlet energy _{(E S1)} is preferred. It is almost difficult to actually measure the higher-order excitation triplet energy in an actual compound, and in reality, it is necessary to use a value calculated by molecular orbital calculation or a model compound. E _Tn _is, E S1 preferably -0.01eV _~ E S1 _-1.00eV, more preferably _{_{E S1 -0.01eV ~ E S1 -0.20eV,}} E S1 -0.01eV ~ E S1 -0.10eV Is even more preferable.

In formula (1), at least one selected from the group consisting of R ¹ and R ³ preferably has a partial structure (D).
At least one selected from the group consisting of R ¹ and R ³ is a partial structure (D).
R ¹ to R ¹¹ which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryls), diheteroarylaminos (where heteroaryls are heteroaryls with 2-12 carbon atoms), aryl heteroarylaminos (where aryls are aryls with 6-12 carbon atoms and heteroaryls have 2 carbon atoms). It is a substituent that is an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms (which is a heteroaryl of to 12), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these may be formed and is substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
R ⁷ and R ⁸ bond to each other at>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ and include b-ring, c-ring and Y A 6-membered ring may be formed
R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 12 carbon atoms). Aryl), diheteroarylamino (where heteroaryl is a heteroaryl having 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is an aryl having 6 to 12 carbon atoms and heteroaryl is an aryl having 2 to 12 carbon atoms). Heteroaryl), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cyano or halogen substituents, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May have been
The R'in>N-R',> C (-R') ₂ and> Si (-R') ₂ is independently an aryl having 6 to 20 carbon atoms and a hetero with 2 to 15 carbon atoms, respectively. More preferably, it is aryl, an alkyl having 1 to 20 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.

In equation (1)
R ² preferably has a partial structure (D).
R ² is the partial structure (D).
R ¹ to R ¹¹ which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl substituent that is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms without substitution, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
Moiety Q is in the structure (D)> C (-R ' ) 2, a partial structure> in _{(D) C (-R')} R in ₂ 'methyl and the partial structure (D) ^{^R} 21 ^~ ^R ²⁸ in When is hydrogen, R ⁶ and R ⁹ in the formula (1) are independently partial structures (D), hydrogen, or aryls having 6 to 30 carbon atoms, heteroaryls having 2 to 30 carbon atoms, respectively. Diarylamino (where aryl is aryl with 6-12 carbon atoms), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms), Heteroaryl is a substituent that is an alkyl having 2 to 12 carbon atoms, an alkyl having 1 to 3 carbon atoms without substitution, or a cycloalkyl having 3 to 20 carbon atoms. Among these substituents, adjacent substitution groups are used. The groups may be bonded to each other to form a ring structure, and at least one hydrogen in these substituents is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl or carbon having 1 to 12 carbon atoms. More preferably, it may be substituted with the number 3 to 20 cycloalkyl.

In equation (1)
At least one selected from the group consisting of R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ preferably has a partial structure (D).
At least one selected from the group consisting of R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ is a partial structure (D).
R ¹ to R ¹¹ which are not partial structures (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms, and among these substituents, adjacent substituents may be bonded to each other to form a ring structure. At least one hydrogen in these may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.
R ⁷ and R ⁸ may be crosslinked at> X ³ to form a 6-membered ring containing b, c and Y, where X ³ is>O,>S,>N-R',> C ( Any one of -R') ₂ or> Si (-R') ₂ , and R ²¹ to R ²⁸ in the partial structure (D) are independently hydrogen or 6 to 30 carbon atoms. Aryl, heteroaryl with 2 to 30 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), diheteroarylamino (where heteroaryl is heteroaryl with 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is heteroaryl with 2 to 12 carbon atoms) However, aryl is an aryl having 6 to 12 carbon atoms, and heteroaryl is a heteroaryl having 2 to 12 carbon atoms), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cyano or halogen. Of these substituents, adjacent substituents may be bonded to each other to form a ring structure, and at least one hydrogen in these substituents is an aryl or carbon having 6 to 30 carbon atoms. It may be substituted with a heteroaryl of number 2 to 30, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.
The R'in>N-R',> C (-R') ₂ and> Si (-R') ₂ is independently an aryl having 6 to 20 carbon atoms and a hetero with 2 to 15 carbon atoms, respectively. More preferably, it is aryl, an alkyl having 1 to 20 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.

The compound of the present invention is preferably a compound represented by any of the following formulas (1-A-1) to (1-A-4).

The compound containing the structure represented by the formula (ii) is preferably a compound represented by any of the following formulas (4-1A) to (4-1D).

At least one hydrogen in the compound having at least one structure represented by the formula (i) may be substituted with cyano, halogen, deuterium, or partial structure (B).

In the above partial structure (B), R ⁴⁰ and R ⁴¹ are independently alkylated, R ⁴⁰ and R ⁴¹ may be bonded to each other, and the total number of carbon atoms of R ⁴⁰ and R ⁴¹ is 2 to 10. The wavy line portion is the binding site with other structures.
In particular, a compound in which at least one hydrogen of the compound represented by the formula (ii) is replaced with a partial structure (B), chlorine, bromine, or iodine is preferably used as the compound of the present invention.

The compounds of the present invention are listed below, but the present invention is not limited to these specific examples.

1-4. Method for producing a compound containing at least one structure represented by the formula (i) A compound containing at least one structure represented by the formula (i) (preferably a compound represented by the formula (1)) is first prepared. An intermediate is produced by binding rings A to C (preferably rings a to c) with a binding group (-X-) (first reaction), and then rings a to c are bonded to the binding group (-X-). The final product can be produced by binding with a group containing X) (second reaction). It is preferable that the binding group (-X-) finally constitutes X ¹ and X ² in the formula (i) or the formula (1), respectively. Here, the case where the binding group is> O will be described.

In the first reaction, general etherification reactions such as nucleophilic substitution reaction and Ullmann reaction can be used. Further, in the second reaction, a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. For details of the first and second reactions, the description given in International Publication No. 2015/102118 can be referred to.

The second reaction is a reaction for introducing B (boron), P (phosphorus) or Si (silicon) that bonds the A ring, the B ring and the C ring. Here, A ring, B ring and C ring is benzene ring which may be either substituted R ^{1 ~} R ¹¹ when it is (a ring in the following scheme (1), b ring and c rings), The reaction for introducing B (boron) will be described. First, the hydrogen atom between the two O's is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium or the like. Next, boron trichloride, boron tribromide, etc. are added, the metal of lithium-boron is exchanged, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem Bora Friedel-Crafts reaction. You can get things. In the second reaction, Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

In the above scheme, lithium was introduced to the desired position by orthometalation, but as in scheme (2) below, a bromine atom or the like was introduced at the position where lithium was to be introduced, and the desired position was also achieved by halogen-metal exchange. Lithium can be introduced.

By appropriately selecting the above-mentioned synthesis method and appropriately selecting the raw material to be used, a compound having a substituent at a desired position and represented by the formula (1) can be synthesized.

Further, for the introduction reaction of Y other than the above, the synthesis method described in Japanese Patent No. 5669163 can be used.

Multimers with single bonds and spacers can be produced by the above synthetic method. Further, it can be produced by synthesizing the monomers and then binding the monomers to each other.

As a compound containing at least one structure represented by the formula (i), a multimer (for example, a compound having a structure represented by the formula (ii)) is basically bonded to each other with each ring structure. The intermediate can be produced in (1st reaction), and then the final product can be produced by bonding each ring structure with a boron atom (2nd reaction). In the first reaction, for example, a general etherification reaction such as a nucleophilic substitution reaction or an Ullmann reaction, or a general amination reaction such as a Buchwald-Hartwig reaction can be used. Further, in the second reaction, a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. The symbols in the structural formulas in the following schemes have the same definitions as those in the formula (ii) or the formula (4).

The second reaction is a reaction for introducing a boron atom that binds each ring structure, as shown in the following scheme (3). First, the hydrogen atoms between X ¹ and X ² and between X ³ and X ⁴ are orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Next, boron trichloride, boron tribromide, etc. are added, the metal of lithium-boron is exchanged, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem Bora Friedel-Crafts reaction. You can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

In particular, the synthesis of dimers is shown below, but multimers of trimers or more can also be produced by the same synthesis method.

In scheme (3), lithium was introduced to a desired position by orthometalation, but as in scheme (4) below, a halogen atom (Hal) was introduced in advance at the position where lithium was to be introduced, and halogen-metal exchange was performed. Can also introduce lithium to the desired position. According to this method, the target product can be synthesized even in a case where orthometalation cannot be performed due to the influence of the substituent, which is useful.

Select synthetic methods described above appropriate, the starting material used also be appropriately selected, having a substituent at the desired ^{^{position, X 1, X 2, X}} 3 and X ⁴ are each independently,> O, or A compound of> NR can be synthesized.

In addition, since the place where the tandem Bora Friedel-Crafts reaction occurs may differ depending on the rotation of the amino group in the intermediate, for example, by-products may be generated. In such a case, the target compound can be isolated from the mixture thereof by chromatography, recrystallization or the like.

Examples of the orthometallation reagent used in the above scheme include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, and lithium hexamethyl. Examples thereof include organic alkaline compounds such as disilamide and potassium hexamethyldisilazide.

Examples of the metal exchange reagent for metal-Y (boron) used in the above scheme include boron halides such as boron trifluoride, trichloride, triiodide, and triiodide, and Y such as CIPN (NET ₂ ) ₂ . Examples thereof include aminated halides, Y alkoxys, and Y aryl bromides.

The blended bases used in the above scheme include N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N, N-. Dimethylaniline, N, N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Examples thereof include Si (where Ar is an aryl such as phenyl).

Lewis acids used in the above scheme include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ , OEt ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , InBr ₃ , In (OTf) ₃ , SnCl. _{_{_{4, SnBr 4, AgOTf, ScCl}}} 3, Sc (OTf) 3, ZnCl 2, ZnBr 2, Zn (OTf) 2, MgCl 2, MgBr 2, Mg (OTf) 2, LiOTf, NaOTf, KOTf, Me 3 SiOTf, Examples thereof include Cu (OTf) ₂ , CuCl ₂ , YCl ₃ , Y (OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , and CoBr ₃ .

In the above scheme, Bronsted bases or Lewis acids may be used to promote the tandem hetero Friedel-Crafts reaction. However, when boron halides such as boron trifluoride, trichloride, tribromide, and triiodide are used, hydrogen fluoride, hydrogen chloride, and hydrogen bromide, as the aromatic electrophobic substitution reaction progresses, Since an acid such as hydrogen iodide is produced, it is effective to use a blended base that captures the acid. On the other hand, when an aminated halide of boron or an alkoxylated of boron is used, it is often necessary to use a blended base because amines and alcohols are produced as the aromatic electrophilic substitution reaction proceeds. However, since the desorption ability of amino groups and alkoxy groups is low, it is effective to use Lewis acid that promotes the desorption.

Further, the compound represented by the formula (ii) or the formula (4) also includes a compound in which at least a part of hydrogen atoms is substituted with cyano, halogen or deuterium, and such a compound is desired. By using a raw material in which the above-mentioned part is cyanated, halogenated, or deuterated, it can be synthesized in the same manner as described above.

1-5. Polymer compound having a repeating unit containing a structure represented by the formula (i) The compound of the present invention is a polymer compound having a repeating unit containing a structure represented by the formula (i) (hereinafter, "high molecular weight of the present invention". It may be referred to as a "molecular compound", and the term "compound of the present invention" may include this polymer compound). Examples of the polymer compound having a repeating unit containing the structure represented by the formula (i) include a compound containing a structure derived from the compound represented by the formula (1) as a repeating unit.
Further, the polymer compound of the present invention may have a triarylamine which may have an unsubstituted or substituent, a fluorene which may have an unsubstituted or substituent, and an anthracene which may have an unsubstituted or substituent. , Tetracene which may have an unsubstituted or substituent, triazine which may have an unsubstituted or substituent, carbazole which may have an unsubstituted or substituent, and which may have an unsubstituted or substituent. Good tetraphenylsilane, spirofluorene which may have an unsubstituted or substituent, triphenylphosphine which may have an unsubstituted or substituent, dibenzothiophene which may have an unsubstituted or substituent, and It is preferable that the repeating unit contains a structure derived from at least one compound selected from the group consisting of dibenzofurene which may have a substituent or a substituent. The repeating unit may be a repeating unit including the structure represented by the formula (i), or may be a repeating unit different from the repeating unit including the structure represented by the formula (i).

The polymer compound of the present invention uses an aryl halide and an arylboronic acid derivative as starting materials, or an arylboroic acid halide derivative, an aryl halide and an arylboronic acid derivative as starting materials by a known method. It can be synthesized by appropriately combining Miyaura coupling, Kumada / Tamao / Collew coupling, Negishi coupling, halide reaction, or boronic acid reaction.

The reactive functional groups of the halide and boronic acid derivative in the Suzuki-Miyaura coupling may be replaced as appropriate, and the functional groups involved in those reactions also in the Kumada-Tamao-Colly coupling and the Negishi coupling. May be swapped. Further, when converting to a Grignard reagent, the metallic magnesium and the isopropyl grinard reagent may be appropriately replaced. The boronic acid ester may be used as it is, or may be hydrolyzed with an acid and used as boronic acid. When used as a boronic acid ester, an alkyl other than those illustrated can be used as the alkyl of the ester portion.

Specific examples of the palladium catalyst used in the reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , Palladium acetate (II): Pd (OAc) ₂ , Tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , Tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba) _3. CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (trit-butylphosphino) palladium (0): Pd (t-Bu ₃ P) ₂ , [1,1 '-Bis (diphenylphosphino) ferrocene] dichloropalladium (II): Pd (dppf) Cl ₂ , [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (1: 1): Pd (dppf) Cl ₂ · CH ₂ Cl ₂ , PdCl ₂ {P (t-Bu) _2- (p-NMe _2- Ph)} ₂ : (A- ^ta Phos) ₂ PdCl ₂ , palladium bis (dibenzylidene) , [1,3-bis (diphenylphosphino) propane] nickel (II) _{_{_{dichloride, PdCl 2 [P (t-}}} Bu) 2 - (p-NMe 2 -Ph)] 2: (A- ta Phos) 2 PdCl ₂ (Pd-132: trademark; manufactured by Johnson Massey).

Further, in order to promote the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (dit-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (dit-butylphosphine) ferrocene, 1- (methoxymethyl) -2- (dit-butylphosphino) ferrocene, 1,1'-bis (dit-butylphosphine) Fino) Ferrocene, 2,2'-bis (dit-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2'-(dit-butylphosphino) -1,1'-binaphthyl, or Examples thereof include 2-dicyclohexylphosphino-2'and 6'-dimethoxybiphenyl.

Specific examples of the bases used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxydo, sodium t-butoxide, sodium acetate, potassium acetate. , Tripotassium phosphate, or potassium fluoride.

Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, anisole, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, tetrahydrofuran, diethyl ether and t-butyl. Methyl ether, 1,4-dioxane, methanol, ethanol, t-butyl alcohol, cyclopentyl methyl ether or isopropyl alcohol, dimethoxyethane, 2- (2-methoxyethoxy) ethane, 2- (2-ethoxyethoxy) ethane, etc. Be done. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

Further, the base may be added as an aqueous solution and reacted in a two-phase system. When the reaction is carried out in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.

When producing the polymer compound of the present invention, it may be produced in one step or in multiple steps. Further, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are placed in the reaction vessel, or it may be carried out by a dropping polymerization method in which the raw materials are added dropwise to the reaction vessel, and the product advances the reaction. It may be carried out by a precipitation polymerization method in which the mixture precipitates, and these can be combined and synthesized as appropriate. For example, when synthesizing the polymer compound of the present invention in one step, a monomer having a polymerizable group bonded to a monomer unit (MU) and a monomer having a polymerizable group bonded to an end cap unit (EC) were added to the reaction vessel. The target product is obtained by reacting in the state. Further, when the polymer compound of the present invention is synthesized in multiple steps, a monomer having a polymerizable group bonded to a monomer unit (MU) is polymerized to a target molecular weight, and then the polymerizable group is bonded to an end cap unit (EC). The desired product is obtained by adding the obtained monomer and reacting.

In addition, the primary structure of the polymer compound can be controlled by selecting the polymerizable group of the monomer. For example, as shown in 1 to 3 of the synthesis scheme (20), a polymer compound having a random primary structure (1 of the synthesis scheme (20)) and a polymer compound having a regular primary structure (synthesis scheme (20)). ) 2 and 3) and the like can be synthesized, and can be used in appropriate combinations according to the target product.

The polymer compound having a repeating unit having a structure represented by the formula (i) may be, for example, a polymer compound having a repeating unit having a structure derived from the compound represented by the formula (1). At this time, a polymer compound may be produced by using a monomer in which a polymerizable group is introduced into R ¹ to R ¹¹ in the formula (1). The substituents as R ¹ to R ¹¹ into which the polymerizable group is introduced are aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls are single bond or linking groups). (The above is the first substituent), and at least one hydrogen in the aryl, the heteroaryl, and the diarylamino is aryl, heteroaryl, alkyl or cycloalkyl (above, It may be substituted with a second substituent). The polymer compound having a repeating unit containing the structure represented by the formula (i) may be produced by using a comonomer in addition to the monomer containing the structure represented by the formula (i). More specifically, the comonomer that may be used in the production of the polymer compound may be one in which a polymerizable group is introduced into any of the following: benzene which may be unsubstituted or substituted, unsubstituted or substituted. With triazine, optionally anthracene, optionally unsubstituted or substituent, triarylamine optionally substituted or substituted, carbazole optionally substituted or substituted, unsubstituted or substituent. Spirofluorene may be unsubstituted or substituted dibenzofuran, unsubstituted or substituted dibenzothiophene, unsubstituted or substituted tetraarylsilane, unsubstituted or optionally substituted triarylphosphine, Unsubstituted or substituted phenoxazine, unsubstituted or substituted phenothiazine, unsubstituted or substituted acridane, unsubstituted or substituted alkyl and unsubstituted or substituted cyclo Alkyl. Among these, benzene which may be unsubstituted or substituted, triarylamine which may have an unsubstituted or substituent, fluorene which may have an unsubstituted or substituent, and an unsubstituted or substituent. Anthracene may be, tetracene which may have an unsubstituted or substituent, triazine which may have an unsubstituted or substituent, benzene which may have an unsubstituted or substituent, and a unsubstituted or substituent. Tetraphenylsilane which may have, spirofluorene which may have an unsubstituted or substituent, triphenylphosphine which may have an unsubstituted or substituent, dibenzo which may have an unsubstituted or substituent Thiophen and dibenzofuran, which may have an unsubstituted or substituent, are preferable, and benzene, biphenyl, terphenyl, triarylamine, triphenyltriazine or carbazole are more preferable. Further, in the above-mentioned phenyl, biphenyl, terphenyl, triarylamine, triphenyltriazine or carbazole, it is more preferable to have an alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms as a substituent.

2. Materials for Organic Devices The compounds of the present invention can also be used as materials for organic devices. Examples of the organic device include an organic electroluminescent device, an organic field effect transistor, and an organic thin film solar cell. Among these, the material for an organic device of the present invention is preferably used as a material for an organic electroluminescent device, and more preferably used as a material for a light emitting layer of a material for an organic electroluminescent device.

2-1. Organic electroluminescent device
2-1-1. Structure of Organic Electroluminescent Device An organic electroluminescent device (organic EL device) includes a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes. The organic EL element may have one or more organic layers in addition to the light emitting layer. Examples of the organic layer include an electron transport layer, a hole transport layer, an electron injection layer, a hole injection layer, and the like, and may further have other organic layers.
FIG. 1 shows an example of the layer structure of an organic electroluminescent device provided with these organic layers.
The organic EL element 100 shown in FIG. 1 is placed on a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. The hole transport layer 104 is provided, the light emitting layer 105 is provided on the hole transport layer 104, the electron transport layer 106 is provided on the light emitting layer 105, and the electron transport layer 106 is provided. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

The organic EL element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107. Above the electron transport layer 106 provided on the electron transport layer 106, the light emitting layer 105 provided on the electron transport layer 106, the hole transport layer 104 provided on the light emitting layer 105, and the hole transport layer 104. The hole injection layer 103 provided in the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be provided.

Not all of the above layers are required, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Further, each of the above layers may be composed of a single layer or a plurality of layers.

As the mode of the layer constituting the organic EL element, in addition to the above-mentioned "board / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", " Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / Anosome / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode "," substrate / "Anofect / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer / electron" Transport layer / cathode ”,“ substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / light emitting layer / electron transport layer / cathode ”,“ substrate / anode The configuration may be "/ light emitting layer / electron transport layer / cathode" or "substrate / anode / light emitting layer / electron injection layer / cathode".

2-1-2. The light emitting layer in the organic electroluminescent device (105 in FIG. 1) is a layer that emits light between electrodes to which an electric field is applied. Typically, the holes injected from the anode 102 and the electrons injected from the cathode 108 are recombined to emit light. The material for forming the light emitting layer may be a compound (luminous compound) that is excited by the recombination of holes and electrons to emit light, and can form a stable thin film shape and is in a solid state. Compounds that exhibit strong emission (fluorescence) efficiency are preferred.
Further, the light emitting layer may be either a single layer or a plurality of layers. Each is formed of a light emitting layer material (host material, dopant material). The host material and the dopant material may be one kind or a combination of two or more. The dopant material may be included in the entire host material, partially, or in any part. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be mixed with the host material in advance and then vapor-deposited at the same time. Further, as will be described later, the light emitting layer can also be formed by a wet film forming method using a light emitting layer forming composition containing a host material and a dopant material.

The compound of the present invention can be preferably used as a material for forming a light emitting layer of an organic electroluminescent device. The compound of the present invention is preferably used as a dopant in the light emitting layer. The compound of the present invention may be used as an emittering dopant in the light emitting layer, or may be used as an assisting dopant.
The compound of the present invention, the host compound, and other components described later may be contained in the same layer, or at least one component may be contained in each of a plurality of layers. The compound of the present invention and the host compound contained in the light emitting layer may be one kind or a combination of two or more. The assisting dopant and the emerging dopant may be contained entirely or partially in the host compound as a matrix. The light emitting layer may be formed by a vapor deposition method, or may be formed by a wet film forming method or the like, in which a paint prepared by dissolving in an organic solvent is applied.

The amount of the compound of the present invention used is preferably large from the viewpoint of high TADF activity and small from the viewpoint of emission spectrum having a narrow half width. The guideline for the amount of the host compound used is preferably 0.001 to 49% by mass, more preferably 0.1 to 40% by mass, and further preferably 0.5 to 25% by mass of the entire material for the light emitting layer. Is.

2-1-2-1. Host Compound A host compound may be used as the light emitting layer containing the compound of the present invention. As the host compound, known compounds can be used, and examples thereof include compounds having at least one of a carbazole ring and a furan ring, among which at least one of furanyl and carbazolyl and at least one of arylene and heteroarylene. It is preferable to use a compound to which is bound. Specific examples include mCP and mCBP.

As the host compound, for example, a compound represented by any of the following formula (H1), formula (H2), formula (H3), formula (H4), and formula (H5) can be used.
These compounds may be polymer compounds having a structure derived from a compound represented by any of the following formulas (H1), (H2), (H3), (H4), and (H5) as a repeating unit. Good.
The organic electroluminescent device of the present invention contains at least one compound represented by the following formulas (H1) to (H5), or has at least one structure in the following (H1) to (H5) as a repeating unit. It is preferable to contain at least one polymer compound.

In formula (H1), L ¹ is an arylene having 6 to 24 carbon atoms, and in formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or 2 to 30 carbon atoms, respectively. At least one hydrogen in the compound represented by each of the above formulas may be substituted with an alkyl, cyano, halogen or heavy hydrogen having 1 to 6 carbon atoms, and in the formula (H3), J Is>O,>S,>N-R',> C (-R') ₂ or> Si (-R') ₂ , and Y is a single bond,>O,>S,> C (- R') ₂ or> Si (-R') ₂ , where Z is CH, CR'or N, and in formula (H4), Z is CH, CR'or N, and R'in>N-R',> C (-R') ₂ ,> Si (-R') ₂ and C-R', respectively, are aryl, heteroaryl, and alkyl, respectively. Alternatively, it is cycloalkyl, and in formula (H5), R ¹ to R ¹¹ are each independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl. It is a substituent, and at least one hydrogen in these substituents may be further substituted with aryl, heteroaryl, diarylamino or alkyl, and adjacent groups of R ¹ to R ¹¹ are bonded to each other to a. Aryl ring or heteroaryl ring may be formed together with the ring, b ring or c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino. Alternatively, it may be substituted with alkyl, at least one hydrogen in these may be further substituted with aryl, heteroaryl, diarylamino or alkyl, and at least one hydrogen in the compound represented by the formula (H5). , Each may be independently substituted with halogen or heavy hydrogen.
As R ¹ to R ¹¹ of the formula (H5), the description of the first substituent and the second substituent substituting the first substituent can be cited.

Further, as the host compound, a compound represented by any of the following formulas (H-1), (H-2) and (H-3) can also be used.

In formulas (H-1), (H-2) and (H-3), L ¹ is an arylene having 6 to 24 carbon atoms, a heteroarylene having 2 to 24 carbon atoms, a heteroarylene allylene having 6 to 24 carbon atoms and It is an arylene heteroarylene arylene having 6 to 24 carbon atoms, preferably an arylene having 6 to 16 carbon atoms, more preferably an arylene having 6 to 12 carbon atoms, and particularly preferably an arylene having 6 to 10 carbon atoms. Examples thereof include divalent groups such as a benzene ring, a biphenyl ring, a terphenyl ring and a fluorene ring. As the heteroarylene, a heteroarylene having 2 to 24 carbon atoms is preferable, a heteroarylene having 2 to 20 carbon atoms is more preferable, a heteroarylene having 2 to 15 carbon atoms is further preferable, and a heteroarylene having 2 to 10 carbon atoms is particularly preferable. Preferably, specifically, a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxazole ring, a thiazazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, Pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, synnoline ring, quinazoline ring , Kinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysin ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolidin ring, furan ring, benzofuran ring, isobenzofuran ring , Dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazan ring, and thiantolen ring.
At least one hydrogen in the compound represented by each of the above formulas may be substituted with alkyl, cyano, halogen or deuterium having 1 to 6 carbon atoms.

The host compound is preferably a compound represented by any of the structural formulas listed below. In the structural formulas listed below, at least one hydrogen may be substituted with halogen, cyano, alkyl having 1 to 4 carbon atoms (for example, methyl or t-butyl), phenyl or naphthyl.

2-1-2-2. Fluorescent material (emitting dopant)
When the compound of the present invention is used as an assisting dopant (assisting dopant in a TAF element), an emulating dopant (emitting dopant in a TAF element) may be used as an additional component of the light emitting layer. The additional component is used for the purpose of narrowing the emission spectrum, improving the color, or extending the life.

The emitting dopant of the present invention is not particularly limited, and a known compound can be used, and can be selected from various materials according to a desired emission color. Specifically, for example, fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysen, benzoxazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazoles. Bistylyl derivatives such as derivatives, oxadiazol derivatives, thiazole derivatives, imidazole derivatives, thiadiazol derivatives, triazole derivatives, pyrazoline derivatives, stillben derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives. (Japanese Patent Laid-Open No. 1-245087), bisstyrylallylen derivative (Japanese Patent Laid-Open No. 2-247278), diazaindacene derivative, furan derivative, benzofuran derivative, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) Isobenzofuran derivatives such as isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7- Cumarin derivatives such as methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives, 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine Derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acrydin derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrolopyridine derivatives, flopyridine derivatives, Examples thereof include 1,2,5-thiadiazolopylene derivatives, pyromethene derivatives, perinone derivatives, pyrolopyrrole derivatives, squarylium derivatives, biolantron derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives.

For example, as blue to blue-green dopant materials for each color-developing light, aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, inden, and chrysen and their derivatives, furan, pyrrole, thiophene, etc. Aromatic complexes such as silol, 9-silafluorene, 9,9'-spirobisilafluolene, benzothiophene, benzofuran, indol, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthylidine, quinoxalin, pyrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stillben derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazol, carbazole, oxazole, oxadiazol, triazole and other azole derivatives and their metal complexes and N , N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine and other aromatic amine derivatives.

Examples of the green to yellow dopant material include a coumarin derivative, a phthalimide derivative, a naphthalimide derivative, a perinone derivative, a pyrolopyrrole derivative, a cyclopentadiene derivative, an acridone derivative, a quinacridone derivative, a naphthacene derivative such as rubrene, and the like. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the compound exemplified as the blue-green dopant material.

Further, as the orange to red dopant material, naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acidimide, perinone derivatives, rare earth complexes such as Eu complex having acetylacetone, benzoylacetone and phenanthroline as ligands, and 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone. Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrolopyridine derivatives, squarylium derivatives, biolantron derivatives, phenazine derivatives, phenoxazone derivatives, thiadiazolopyrene derivatives, etc. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the compound.

In addition, as the additional component, it can be appropriately selected and used from the compounds described in the June 2004 issue of Chemical Industry, page 13, and the references mentioned therein.

An amine having a stilbene structure is represented by, for example, the following formula.

In the formula, Ar ¹ is an m-valent group derived from an aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, but Ar ¹ to Ar. ^At least one of ³ has a stillben structure, Ar ¹ to Ar ³ may be substituted, and m is an integer of 1 to 4.

The amine having a stilbene structure is more preferably diaminostilbene represented by the following formula.

In the formula, Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

Specific examples of aryls having 6 to 30 carbon atoms are benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluorene, triphenylene, pyrene, chrysene, naphthalene, perylene, stilben, distyrylbenzene, distyrylbiphenyl, and distyryl. Fluorene can be mentioned.

Specific examples of amines having a stilbene structure are N, N, N', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, N, N, N', N'-tetra (1-naphthyl). ) -4,4'-diaminostilbene, N, N, N', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N'-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthril) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) stilbene] -biphenyl, 1,4-bis [4'-bis (diphenylamino) stilbene] -benzene, 2,7-bis [4'-bis (diphenylamino) stilbene] -9,9-dimethyl Examples thereof include fluorene, 4,4'-bis (9-ethyl-3-carbazovinylene) -biphenyl, and 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl.
Further, amines having a stilbene structure described in JP-A-2003-347056 and JP-A-2001-307884 may be used.

Examples of the perylene derivative include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, and 3,4-. Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene , 3- (9'-anthril) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di (t-butyl) perylenel) and the like.
In addition, JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A-2000-34234, JP-A-2001-267075, JP-A-2001-217077, and the like may be used.

Examples of the compound used as the emitting dopant include compounds containing a boron atom, for example, a borane derivative, a dioxaboronaftanthracene (DOBNA) derivative and a multimer thereof, a diazaboronaftanthracene (DABNA) derivative and the like. Multimers, oxavolanaft anthracene (OABNA) derivatives and their multimers, oxabolanaft anthracene (OBNA) derivatives and their multimers, azaboranaft anthracene (ABNA) derivatives and their multimers, trioxaborazibenzopyrene derivatives and Examples thereof include the multimer, the dioxaazabora benzopyrene derivative and its multimer, the oxadiazabora benzopyrene derivative and its multimer, and the like.

Examples of borane derivatives include 1,8-diphenyl-10- (dimethylboryl) anthracene, 9-phenyl-10- (dimethylboryl) anthracene, 4- (9'-anthril) dimesitytylborylnaphthalene, and 4- (10'). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4'-(N-carbazolyl) phenyl) -10- (Dimethylboryl) Anthracene and the like.
Moreover, the borane derivative described in International Publication No. 2000/40586 etc. may be used.

The aromatic amine derivative is represented by, for example, the following formula.

In the formula, Ar ⁴ is an n-valent group derived from an aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are independently aryls having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ are independently. It may be substituted and n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene, Ar ⁵ and Ar ⁶ are independently aryls having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ are respectively. May be substituted, and n is 2, aromatic amine derivatives are more preferred.

Specific examples of aryls having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorenephenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthalene, perylene, and pentacene.

As the aromatic amine derivative, as a chrysen system, for example, N, N, N', N'-tetraphenylcrisen-6,12-diamine, N, N, N', N'-tetra (p-tolyl) Chrysen-6,12-diamine, N, N, N', N'-tetra (m-tolyl) Chrysen-6,12-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) chrysen -6,12-diamine, N, N, N', N'-tetra (naphthalen-2-yl) chrysen-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis ( 4-isopropylphenyl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) chrysen-6,12-diamine, N, N'-bis (4) -Isopropylphenyl) -N, N'-di (p-tolyl) chrysen-6,12-diamine and the like can be mentioned.

As the pyrene system, for example, N, N, N', N'-tetraphenylpyrene-1,6-diamine, N, N, N', N'-tetra (p-tolyl) pyrene-1,6 -Diamine, N, N, N', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N', N'-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) pyrene-1 , 6-Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) Pyrene-1,6-diamine, N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (3,4-dimethylphenyl) -3,8-diphenylpyrene-1,6 -Diamine, N, N, N, N-Tetraphenylpyrene-1,8-diamine, N, N'-bis (biphenyl-4-yl) -N, N'-diphenylpyrene-1,8-diamine, N ¹ , N ⁶ -diphenyl-N ¹ , N ⁶ -bis- (4-trimethylsilanyl-phenyl) -1H, 8H-pyrene-1,6-diamine and the like can be mentioned.
For example, specific examples include formulas (PYR1), (PYR2), (PYR3) and (PYR4).

The anthracene system includes, for example, N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N', N'-tetra (p-tolyl) anthracene-9,10-diamine. , N, N, N', N'-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene- 9,10-Diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) anthracene-9,10-diamine, N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N, N', N'-tetra (p-tolyl) anthracene-9,10-diamine , 2,6-di-t-butyl-N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N'-bis (4-isopropylphenyl) -N , N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N'-bis (4-isopropylphenyl) -N, N'-bis (4-t-butylphenyl) ) Anthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis (4-di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4) -Di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-) Examples thereof include 1-naphthyl) anthracene and 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene.

In addition, [4- (4-diphenylamino-phenyl) naphthalene-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalene-2-yl] -diphenylamine, 4,4' -Bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-Terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, indolocarbazole derivatives and the like.
Further, the aromatic amine derivative described in JP-A-2006-156888 may be used.

The indolocarbazole derivative is a compound represented by the following formula (IDC1). Specific examples thereof include compounds having the following partial structures (IDC11), (IDC12) and (IDC13). In the formula (IDC1) below, Z is CR _A or N, and π1 and π2 are independently substituted or unsubstituted aromatic hydrocarbons having 6 to 50 carbon atoms or substituted or substituted, respectively. an unsubstituted aromatic heterocyclic ring carbon atoms _{5 ~ 50, R a, R} B and R _C are hydrogen and any substituent, n and m are each independently an integer of 1 to 4 There, two adjacent R _a, may form R _B and R _C are substituted or unsubstituted ring structure bonded to each other. More specifically, the formulas (IDC121), (IDC131), (IDC132), (IDC133), (IDC134) and the like can be mentioned.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Further, the coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876, JP-A-6-298758 and the like may be used.

Examples of the pyran derivative include the following DCM and DCJTB.

Further, JP-A-2005-126399, JP-A-2005-097283, JP-A-2002-234892, JP-A-2001-220577, JP-A-2001-081090, and JP-A-2001-052869. The pyran derivative described in the above may be used.

Further, the phosphor used in the present invention is preferably a compound having a boron atom. As compounds having a boron atom used as a phosphor, dioxaboronaftanthracene (DOBNA) derivative and its multimer, diazaboronaftanthracene (DABNA) derivative and its multimer, oxaazaboronaftanthracene (OABNA) derivative and Examples thereof include the multimer, an oxabolanaft anthracene (OBNA) derivative and its multimer, and an azaboronaft anthracene (ABNA) derivative and its multimer.

As the eliminating dopant, it is also preferable to use at least one compound represented by the following formulas (ED1), (ED1') and (ED2).

(In formula (ED1),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, respectively. Aryloxy, or diallylboryl (two aryls may be attached via a single bond or a linking group), which may be further substituted with aryl, heteroaryl or alkyl, and R ¹ Adjacent groups of ~ R ³ , R ⁴ to R ⁶ and R ⁹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring. The rings are substituted with aryl, heteroaryl, diallylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls may be attached via a single bond or a linking group). Also, these may be further substituted with aryl, heteroaryl or alkyl,
X is> O or> N-R, and R and R ¹³ of said> N-R are aryl, heteroaryl or alkyl, which may be substituted with aryl, heteroaryl or alkyl.
However, when X is an amino group, R ² does not become an amino group,
And
At least one hydrogen in the compound and structure represented by the formula (ED1) may be substituted with cyano, halogen or deuterium. )

(In the formula (ED1'),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independent hydrogen, respectively. Aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls may be attached via a single bond or a linking group), which are further aryl, hetero. may be substituted by aryl or alkyl ^{^{^{^{and, R 1 ~ R 3, R}}}} 4 ~ R 7, a ring adjacent groups are bonded to one of R 8 ^{~ R 10} and ^R 11 ^{~ R 14,} Aryl rings or heteroaryl rings may be formed with rings b, c or d, and the formed rings are aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl ( The two aryls may be substituted with a single bond or a linking group), and these may be further substituted with aryl, heteroaryl or alkyl.
X is> O or> N-R, said R of> N-R is aryl, heteroaryl or alkyl, which may be substituted with aryl, heteroaryl or alkyl.
L is a single bond,> CR ₂ ,>O,> S and> N-R, and R in the above> CR ₂ and> N-R are independently hydrogen, aryl, heteroaryl, and diarylamino. , Alkoxy, alkoxy, aryloxy, or diallylboryl (two aryls may be attached via a single bond or a linking group), which may be further substituted with aryl, heteroaryl or alkyl. ,
And
At least one hydrogen in the compound and structure represented by the formula (ED1') may be substituted with cyano, halogen or deuterium. )

(In formula (ED2),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independent hydrogen, respectively. Aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, diarylboryl (two aryls may be attached via a single bond or a linking group). , Heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silyls, wherein at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl and also R ⁵ to R ⁷ and R ¹⁰ to. Adjacent groups of R ¹² may be bonded to each other to form an aryl ring or a heteroaryl ring together with a b ring or a d ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, or diaryl. Amino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, diarylboryl (two aryls may be attached via a single bond or a linking group), heteroaryloxy, arylthio , Heteroarylthio or alkyl-substituted silyls, at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl.
X ¹ , X ² , X ³ and X ⁴ are independently>O,> NR or> CR ₂ , and the R of> NR and the R of> CR ₂ have 6 carbon atoms. It is an aryl of -12, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms, and the R of> N-R and the R of> CR ₂ are -O-, -S-,-. It may be bonded to at least one of the a ring, b ring, c ring and d ring by C (-R) _2- or a single bond, and R of the -C (-R) _2- is hydrogen or carbon number. It is an alkyl of 1 to 6 and
However, of X ¹ , X ² , X ³ , and X ⁴ ,> O is 2 or less.
And
At least one hydrogen in the compound represented by the formula (ED2) may be substituted with cyano, halogen or deuterium. )

More specifically, the following formulas (ED11) to (ED19), (ED21) to (ED27), (ED211), (ED212), (ED221) to (ED223), (ED231), (ED241), (ED242) ), (ED261) and (ED271) can be mentioned.

Equations (ED11) to (ED19), (ED21) to (ED27), (ED211), (ED212), (ED221) to (ED223), (ED231), (ED241), (ED242), (ED261) and (ED21) At least one hydrogen in the structure represented by ED271) is independently aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diarylboryl (two aryls are single bond or linking groups). They may be substituted with (may be attached via), and these may be further substituted with aryl, heteroaryl or alkyl. For preferred ranges and specific examples of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy and diarylboryl (two aryls may be attached via a single bond or a linking group). The corresponding description in R ¹ to R ¹¹ of (1) can be referred to.
The phosphor as an additional component is preferably a compound having at least one substituent selected from the following substituent group B, and formulas (ED11) to (ED19) and (ED21) to (ED27). , (ED211), (ED212), (ED221) to (ED223), (ED231), (ED241), (ED242), (ED261) or (ED271), and in that structure It is more preferable that the compound has a structure in which at least one structure selected from the substituent group B is bonded to the benzene ring (including the benzene ring constituting the condensed ring). In the following structural formula, "Me" represents methyl, "tBu" represents t-butyl, "tAm" represents t-amyl, "tOct" represents t-octyl, and * represents the binding position.

Substituent group B:

2-1-2-3. Assisting Dopant (heat-activated delayed phosphor)
The assisting dopant (thermoactive delayed phosphor: TADF compound) that can be used when the compound of the present invention is used as an emtituting dopant (ED) in a TAF element includes an electron-donating substituent called a donor and an acceptor. Localize HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) in the molecule using so-called electron-accepting substituents so that efficient reverse intersystem crossing occurs. It is preferably a donor-acceptor type TADF compound (DA type TADF compound) designed in.
Here, the term "electron-donating substituent" (donor) as used herein means a substituent and a partial structure in which the HOMO orbital is localized in the TADF compound molecule, and means "electron-accepting substituent". The term "group" (acceptor) means a substituent and a partial structure in which the LUMO orbital is localized in the TADF compound molecule.
In general, TADF compounds using donors and acceptors have a large spin-orbit coupling (SOC) due to their structure, a small exchange interaction between HOMO and LUMO, and a small ΔE (ST). In addition, a very fast intersystem crossing speed is obtained. On the other hand, TADF compounds using donors and acceptors have greater structural relaxation in the excited state (for some molecules, the stable structure differs between the ground state and the excited state, so conversion from the ground state to the excited state by an external stimulus is performed. After that, the structure changes to a stable structure in the excited state), and since it gives a wide emission spectrum, it may reduce the color purity when used as a light emitting material.

As an assisting dopant that can be used when the compound of the present invention is used as an ED in a TAF device, for example, a compound in which a donor and an acceptor are directly bonded or via a spacer can be used. As the donor-like and acceptor-like structures used in the heat-activated delayed phosphor, for example, the structures described in Chemistry of Materials, 2017, 29, 1946-1963 can be used. As donor structures, carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenyldihydroindrocarbazole, phenylbicarbazole, bicarbazole, turcarbazole , Diphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacrine, diphenylamine, bis (tert-butyl) phenylamine, (diphenylamino) phenyldiphenylbenzenediamine, dimethyltetraphenyldihydroaclydin Examples include diamine, tetramethyl-dihydro-indenoaclydin and diphenyl-dihydrodibenzoazacillin. Acceptable structures include sulfonyldibenzene, benzophenone, phenylenebis (phenylmethanone), benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, benzenetricarbonitrile, triazole, oxazole, and thiaxazole. , Benzenethiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzoimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthonedioxide, dimethylanthracenone, anthracendione, cycloheptabipyridine, full orange carbonitrile, Triphenyltriazine, pyrazinedicarbonitrile, pyrimidine, phenylpyrimidine, methylpyrimidine, pyridinedicarbonitrile, dibenzoquinoxaline dicarbonitrile, bis (phenylsulfonyl) benzene, dimethylthioxanthene dioxide, thianslentetraoxide and tris (dimethylphenyl) ) Benzene is mentioned. In particular, the compound having the thermoactive delayed fluorescence of the present invention has, as a partial structure, carbazole, phenoxazine, aclysine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, It is preferably a compound having at least one selected from oxadiazole, thiaziazole and benzophenone.

The compound used as the assisting dopant is preferably a thermally active delayed phosphor, and the emission spectrum thereof preferably overlaps at least a part of the absorption peak of the emitting dopant. Hereinafter, compounds that can be used as the assisting dopant for the light emitting layer of the present invention will be exemplified. However, the compound that can be used as an assisting dopant in the present invention is not limitedly interpreted by the following exemplified compounds, and in the following formula, Me represents methyl and t-Bu represents t-butyl. , Ph represents phenyl, and wavy lines represent bonding positions.

Further, as the heat-activated delayed phosphor, a compound represented by any of the following formulas (AD1), (AD2) and (AD3) can also be used.

In formulas (AD1), (AD2) and (AD3),
M are independently single-bonded, -O-,> N-Ar or> CAR ₂ , and are of the HOMO depth and excited singlet energy level and excited triplet energy level of the substructure to be formed. From a height standpoint, it is preferably single bond, —O— or> N—Ar. J is a spacer structure that separates the donor substructure and the acceptor substructure, each of which is an arylene having 6 to 18 carbon atoms, and is a conjugate that exudes from the donor substructure and the acceptor substructure. From the viewpoint of the size of the acceptor, an acceptor having 6 to 12 carbon atoms is preferable. More specifically, phenylene, methylphenylene and dimethylphenylene can be mentioned. Q is independently = C (-H)-or = N-, and is a viewpoint of the shallowness of LUMO and the height of the excited singlet energy level and the excited triplet energy level of the formed partial structure. Therefore, preferably = N−. Ar is a partial structure formed independently of hydrogen, an aryl having 6 to 24 carbon atoms, a heteroaryl having 2 to 24 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 18 carbon atoms. From the viewpoint of the depth of HOMO and the height of the excited single-term energy level and the excited triple-term energy level, hydrogen, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 14 carbon atoms, and a carbon number of carbon atoms are preferable. It is an alkyl of 1 to 4 or a cycloalkyl of 6 to 10 carbon atoms, more preferably hydrogen, phenyl, tolyl, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazil, carbazolyl, dimethylcarbazolyl, di-tert-butyl. Carbazolyl, benzoimidazole or phenylbenzoimidazole, more preferably hydrogen, phenyl or carbazolyl. m is 1 or 2. n is an integer of 2 to (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance. Further, at least one hydrogen in the compound represented by each of the above formulas may be substituted with halogen or deuterium.

More specifically, the compound used as the second component of the light emitting layer of the present invention is 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, Cz-TRZ3, BDPCC-TPTA, MA-TA, PA. -TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTRz, spiroAC-TRZ, Ac-HPM, Ac-PPM, Ac-MPM, TCzTrz, TmCzTrz and DCzmCzTrz are preferable.

2-1-3. The electron injection layer and the electron transport layer in the organic electroluminescent device The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting the electrons injected from the cathode 108 or the electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are formed by laminating and mixing one or more kinds of electron transport / injection materials, respectively. The electron transport layer 106 and the electron injection layer 107 may be formed by a mixture of the electron transport / injection material and the polymer binder.

The electron injection / transport layer is a layer in which electrons are injected from the cathode and is in charge of further transporting electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For that purpose, it is preferable that the substance has a high electron affinity, a high electron mobility, excellent stability, and is less likely to generate trap impurities during production and use. However, when considering the transport balance between holes and electrons, the electron transport capacity is so high when it mainly plays a role of efficiently blocking the holes from the anode from flowing to the cathode side without recombination. Even if it is not high, it has the same effect of improving luminous efficiency as a material having high electron transport capacity. Therefore, the electron injection / transport layer in the present embodiment may also include the function of a layer capable of efficiently blocking the movement of holes.

As the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, it is used as a compound conventionally used as an electron transfer compound in a photoconductive material, an electron injection layer and an electron transport layer of an organic EL element. It can be arbitrarily selected and used from the known compounds known.

The material used for the electron transport layer or the electron injection layer is a compound composed of an aromatic ring or a complex aromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus. It is preferable to contain at least one selected from a pyrrole derivative, a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, fused ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives typified by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , Kinone derivatives such as anthraquinone and diphenoquinone, phosphine oxide derivatives, arylnitrile derivatives and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes. These materials may be used alone, but may be mixed with different materials.

Specific examples of other electron transfer compounds include borane derivatives, pyridine derivatives, naphthalene derivatives, fluorantene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, and anthraquinone derivatives. , Diphenoquinone derivative, Diphenylquinone derivative, Perylene derivative, Oxaziazole derivative (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), Thiophen derivative, Triazole derivative (N- Naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol-based metal complexes, quinoxalin derivatives, quinoxalin derivative polymers, benzazole compounds, gallium complexes, pyrazole derivatives, Perfluoroylated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline derivative (2,2'-bis (benzo [h] quinoline-2-yl) -9,9'-spirobifluorene, etc.), imidazole pyridine derivative, benzo Imidazole derivatives (tris (N-phenylbenzoimidazole-2-yl) benzene, etc.), benzoxazole derivatives, thiazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as telpyridine, bipyridine derivatives, telpyridine derivatives (1,3- Bis (4'-(2,2': 6'2 "-terpyridinyl)) benzene, etc.), naphthylidine derivatives (bis (1-naphthyl) -4- (1,8-naphthylidine-2-yl) phenylphosphine oxide, etc." ), Ardazine derivative, pyrimidine derivative, arylnitrile derivative, indole derivative, phosphine oxide derivative, bisstyryl derivative, silol derivative, azoline derivative and the like.

Further, a metal complex having electron-accepting nitrogen can also be used. For example, hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes can be used. Can be mentioned.

The above-mentioned materials can be used alone, but they may be mixed with different materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluorantene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol derivatives Metal derivatives are preferred.

<Borane derivative>
The borane derivative is, for example, a compound represented by the following formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.

In formula (ETM-1), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, respectively. At least one of the rings, or cyanos, R ¹³ to R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. , X are optionally substituted arylene, Y is optionally substituted aryl having 16 or less carbon atoms, substituted boron, or optionally substituted carbazolyl, and n. Are independently integers from 0 to 3. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl and cycloalkyl.

Among the compounds represented by the formula (ETM-1), the compound represented by the following formula (ETM-1-1) and the compound represented by the following formula (ETM-1-2) are preferable.

In formula (ETM-1-1), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. At least one of the containing heterocycles, or cyano, R ¹³ to R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. R ²¹ and R ²² are independently of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. At least one, X ¹ is an arylene having 20 or less carbon atoms which may be substituted, n is an integer of 0 to 3 independently, and m is 0 to 4 independently. Is an integer of. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl and cycloalkyl.

In formula (ETM-1-2), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. At least one of the contained heterocycles, or cyano, R ¹³ to R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. X ¹ is an arylene having 20 or less carbon atoms which may be substituted, and n is an integer of 0 to 3 independently. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl and cycloalkyl.

Specific examples of X ¹ include divalent groups represented by any of the following formulas (X-1) to (X-9).

(In each formula, ^Ra is an independently alkyl, cycloalkyl or optionally substituted phenyl, and * represents the bond position.)

Specific examples of this borane derivative include the following compounds.

This borane derivative can be produced by using a known raw material and a known synthesis method.

<Pyridine derivative>
The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by the formula (ETM-2-1) or the formula (ETM-2-2).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.

In the formula (ETM-2-1), R ¹¹ to R ¹⁸ are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). ) Or aryl (preferably aryl with 6 to 30 carbon atoms).

In the formula (ETM-2-2), R ¹¹ and R ¹² are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). ) Or aryl (preferably aryl having 6 to 30 carbon atoms), and R ¹¹ and R ¹² may be bonded to form a ring.

In each formula, the "pyridine-based substituent" is any of the following formulas (Py-1) to (Py-15) (* in the formula represents a bond position), and the pyridine-based substituent is Each may be independently substituted with an alkyl having 1 to 4 carbon atoms. Further, the pyridine-based substituent may be bonded to φ, anthracene ring or fluorene ring in each formula via a phenylene group or a naphthylene group.

The pyridine-based substituent is any of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44) (formula). * In the inside represents the bonding position.).

At least one hydrogen in each pyridine derivative may be substituted with deuterium, and of the two "pyridine-based substituents" in the above formula (ETM-2-1) and formula (ETM-2-2). One may be replaced with aryl.

The "alkyl" in R ¹¹ to R ¹⁸ may be either a straight chain or a branched chain, and examples thereof include a linear alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicocil.

As the alkyl having 1 to 4 carbon atoms to be substituted with the pyridine-based substituent, the above description of the alkyl can be cited.

Examples of the "cycloalkyl" in R ¹¹ to R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms.
Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the "aryl" in R ¹¹ to R ¹⁸ , a preferable aryl is an aryl having 6 to 30 carbon atoms, a more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms. Yes, and particularly preferably an aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, which is a monocyclic aryl, (1-, 2-) naphthyl, which is a fused dicyclic aryl, and acenaphthylene-, which is a condensed tricyclic aryl. 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2) -, 3-, 4-, 9-) phenanthryl, triphenylene- (1-, 2-) yl, which is a fused tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-) , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl and the like. ..

Preferred "aryls having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, and particularly preferably phenyl, 1 Includes -naphthyl or 2-naphthyl.

R ¹¹ and R ¹² in the above formula (ETM-2-2) may be combined to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, etc. are included in the 5-membered ring of the fluorene skeleton. Cyclohexane, fluorene, indene and the like may be spiro-bonded.

Specific examples of this pyridine derivative include the following compounds.

This pyridine derivative can be produced by using a known raw material and a known synthesis method.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

In formula (ETM-3), X ¹² to X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted hetero. Represents aryl. Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Specific examples of this fluoranthene derivative include the following compounds. In the following formula, Me represents methyl.

<BO derivative>
The BO derivative is, for example, a multimer of a polycyclic aromatic compound represented by the following formula (ETM-4) or a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).

R ⁶¹ to R ⁷¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, or diallylboryl (two aryls). It may be attached via a single bond or a linking group), and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, adjacent groups of R ⁶¹ to R ⁷¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring. Aryl, Heteroaryl, Diarylamino, Diheteroarylamino, Arylheteroarylamino, Alkyl, Cycloalkyl, Aryl, Aryloxy, or Arylboryl (even if the two aryls are attached via a single bond or a linking group) It may be substituted with (may), and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, at least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.

For the explanation of the substituent and the form of ring formation in the formula (ETM-4), the description of the polycyclic aromatic compound represented by the formula (1) or the formula (2) can be cited.

Specific examples of this BO-based derivative include the following compounds.

This BO-based derivative can be produced by using a known raw material and a known synthesis method.

<Anthracene derivative>
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).

Ar is independently divalent benzene or naphthalene, and R ¹ to R ⁴ are independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or carbon number of carbon atoms. 6 to 20 aryls.

Ar can be independently selected from divalent benzene or naphthalene, and the two Ars may be different or the same, but they are the same from the viewpoint of ease of synthesis of the anthracene derivative. Is preferable. Ar binds to pyridine to form a "site consisting of Ar and pyridine", and this site is anthracene as a group represented by any of the following formulas (Py-1) to (Py-12), for example. Is bound to. * In the formula below represents the bond position.

Among these groups, the group represented by any of the formulas (Py-1) to (Py-9) is preferable, and the group is represented by any of the formulas (Py-1) to (Py-6). Groups are more preferred. The two "sites composed of Ar and pyridine" that bind to anthracene may have the same or different structures, but are preferably the same structure from the viewpoint of ease of synthesis of the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two "sites composed of Ar and pyridine" are the same or different.

The alkyl having 1 to 6 carbon atoms in R ¹ to R ⁴ may be either a straight chain or a branched chain. That is, it is a straight chain alkyl having 1 to 6 carbon atoms or a branched chain alkyl having 3 to 6 carbon atoms. More preferably, it is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, Examples thereof include 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. , Methyl, ethyl, or t-butyl is more preferred.

Specific examples of cycloalkyl having 3 to 6 carbon atoms in R ¹ to R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

As for the aryl having 6 to 20 carbon atoms in R ¹ to R ^4, the aryl having 6 to 16 carbon atoms is preferable, the aryl having 6 to 12 carbon atoms is more preferable, and the aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of "aryl having 6 to 20 carbon atoms" include phenyl, which is a monocyclic aryl, (o-, m-, p-) trill, and (2,3-,2,4-,2,5-). , 2,6-, 3,4-, 3,5-) xsilyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2) -, 3-, 4-) Biphenylyl, fused bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl terphenyl (m-terphenyl-2'-yl, m-terphenyl-4) '-Il, m-terphenyl-5'-il, o-terphenyl-3'-il, o-terphenyl-4'-il, p-terphenyl-2'-il, m-terphenyl-2 -Il, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p- Terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused tricyclic aryl, anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) il, phenalen- (1-, 2-) il, (1-, 2-) 2-, 3-, 4-, 9-) phenanthril, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1) Examples thereof include-, 2-, 5-) yl and perylene- (1-, 2-, 3-) yl, which is a condensed pentacyclic aryl.

Preferred "aryl of 6-20 carbons" are phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl. More preferably, it is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Ar ¹ is independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

Ar ² is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaftyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

R ¹ to R ⁴ are independently hydrogen, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 20 carbon atoms, and are represented by the formula (ETM-5-1). The explanation can be quoted.

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced using known raw materials and known synthetic methods.

<Benzofluorene derivative>
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Ar ¹ is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaftyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

Ar ² is independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). ), and the two Ar ² may form a ring.

The "alkyl" in Ar ² may be either a straight chain or a branched chain, and examples thereof include a linear alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like can be mentioned.

Examples of the "cycloalkyl" in Ar ² include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms. Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the "aryl" in Ar ² , a preferable aryl is an aryl having 6 to 30 carbon atoms, a more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms, particularly. It is preferably an aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentasenyl and the like.

Two Ar ² may form a ring, as a result, the 5-membered ring of the fluorene skeleton, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-linked You may.

Specific examples of this benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced by using a known raw material and a known synthesis method.

<Phosphine oxide derivative>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/07927 and International Publication No. 2013/079678.

R ⁵ is a substituted or unsubstituted alkyl of 1 to 20 carbon atoms, heteroaryl of aryl or 5 to 20 carbon atoms of 6 to 20 carbon atoms,
R ⁶ is CN, substituted or unsubstituted, alkyl having 1 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 5 to 20 carbon atoms, and 1 to 20 carbon atoms. 20 alkoxy or aryloxy with 6 to 20 carbon atoms,
R ⁷ and R ⁸ are independently substituted or unsubstituted aryls having 6 to 20 carbon atoms or heteroaryls having 5 to 20 carbon atoms, respectively.
R ⁹ is oxygen or sulfur
j is 0 or 1, k is 0 or 1, r is an integer of 0-4, and q is an integer of 1-3.

The phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).

R ¹ to R ³ may be the same or different, hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, arylether group, arylthioether group, aryl, heterocyclic group, halogen. , Cyano, aldehyde, carbonyl, carboxyl, amino, nitro, silyl, and fused rings formed between adjacent substituents.

Ar ¹ may be the same or different and is an arylene or heteroaryl group, and Ar ² may be the same or different and is an aryl or heteroaryl. However, at least one of Ar ¹ and Ar ² has a substituent or forms a fused ring with an adjacent substituent. n is an integer of 0 to 3, and when n is 0, the unsaturated structure portion does not exist, and when n is 3, R ¹ does not exist.

Among these substituents, alkyl means, for example, a saturated aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, etc., which may be unsubstituted or substituted. The substituent when substituted is not particularly limited, and examples thereof include alkyl, aryl, and heterocyclic groups, and this point is also common to the following description. The number of carbon atoms of the alkyl is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

Further, the cycloalkyl means, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may be substituted or substituted. The number of carbon atoms in the alkyl moiety is not particularly limited, but is usually in the range of 3 to 20.

Further, aralkyl refers to an aromatic hydrocarbon group mediated by an aliphatic hydrocarbon such as benzyl or phenylethyl, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be substituted or substituted. Absent. The carbon number of the aliphatic portion is not particularly limited, but is usually in the range of 1 to 20.

Further, the alkenyl indicates an unsaturated aliphatic hydrocarbon group containing a double bond such as vinyl, allyl, butadienyl, etc., which may be substituted or substituted. The carbon number of the alkenyl is not particularly limited, but is usually in the range of 2 to 20.

Further, the cycloalkenyl refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl, a cyclopentadienyl, or a cyclohexenyl group, which may be unsubstituted or substituted. ..

Further, alkynyl indicates an unsaturated aliphatic hydrocarbon group containing a triple bond such as acetylenyl, which may be unsubstituted or substituted. The carbon number of alkynyl is not particularly limited, but is usually in the range of 2 to 20.

Further, the alkoxy indicates an aliphatic hydrocarbon group via an ether bond such as methoxy, and the aliphatic hydrocarbon group may be substituted or substituted. The number of carbon atoms of the alkoxy is not particularly limited, but is usually in the range of 1 to 20.

Alkoxythio is a group in which the oxygen atom of the ether bond of alkoxy is replaced with a sulfur atom.

Further, the aryl ether group indicates, for example, an aromatic hydrocarbon group via an ether bond such as phenoxy, and the aromatic hydrocarbon group may be substituted or substituted. The number of carbon atoms of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

Further, the arylthioether group is a group in which the oxygen atom of the ether bond of the arylether group is replaced with a sulfur atom.

Aryl means, for example, an aromatic hydrocarbon group such as phenyl, naphthyl, biphenylyl, phenanthryl, terphenylyl, and pyrenyl. Aryl may be unsubstituted or substituted. The number of carbon atoms of the aryl is not particularly limited, but is usually in the range of 6 to 40.

Further, the heterocyclic group refers to a cyclic structural group having an atom other than carbon such as furanyl, thiophenyl, oxazolyl, pyridyl, quinolinyl, and carbazolyl, which may be unsubstituted or substituted. The number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen refers to fluorine, chlorine, bromine, and iodine.

Aldehydes, carbonyls, and aminos can also contain groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

In addition, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be substituted or substituted.

The silyl indicates a silicon compound group such as trimethylsilyl, which may be unsubstituted or substituted. The carbon number of silyl is not particularly limited, but is usually in the range of 3 to 20. The number of silicon is usually 1 to 6.

The fused rings formed between the adjacent substituents are, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , and Ar ¹ . It is a conjugated or non-conjugated fused ring formed between Ar ² and the like. Here, when n is 1, may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These fused rings may contain nitrogen, oxygen, and sulfur atoms in the ring structure, or may be condensed with another ring.

Specific examples of this phosphine oxide derivative include the following compounds.

This phosphine oxide derivative can be produced by using a known raw material and a known synthesis method.

<Pyrimidine derivative>
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-Il, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) Phenantril, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and for example, the above-mentioned aryl and heteroaryl may be substituted, respectively.

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced by using a known raw material and a known synthesis method.

<Aryl nitrile derivative>
The arylnitrile derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which a plurality of the compounds are bonded by a single bond or the like. Details can be found in US Application Publication No. 2014/0197386.

Ar _ni preferably has a large number of carbon atoms from the viewpoint of fast electron transportability, and preferably has a small number of carbon atoms from the viewpoint of high T1. Specifically, Ar _ni is preferably a high T1 for use in a layer adjacent to the light emitting layer, is an aryl having 6 to 20 carbon atoms, and is preferably an aryl having 6 to 14 carbon atoms, more preferably. It is an aryl having 6 to 10 carbon atoms. Further, the number of nitrile substitutions n is preferably large from the viewpoint of high T1 and preferably small from the viewpoint of high S1. Specifically, the number of substitutions n of nitrile is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. From the viewpoint of high S1 and high T1, donor heteroaryls are preferable, and donor heteroaryls are preferably small because they are used as an electron transport layer. From the viewpoint of charge transportability, aryl or heteroaryl having a large number of carbon atoms is preferable, and it is preferable to have a large number of substituents. Specifically, the number of substitutions m of Ar is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 to 2.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatinyl, thiantranyl, indridinyl and the like.

The arylnitrile derivative may be a multimer in which a plurality of compounds represented by the formula (ETM-9) are bonded by a single bond or the like. In this case, in addition to the single bond, an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring) may be bonded.

Specific examples of this arylnitrile derivative include the following compounds.

This arylnitrile derivative can be produced using a known raw material and a known synthesis method.

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/015601.

Specific examples of this triazine derivative include the following compounds.

This triazine derivative can be produced using a known raw material and a known synthesis method.

<Benzimidazole derivative>
The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenanthrene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. Yes, in the "benzimidazole-based substituent", pyridyl in the "pyridine-based substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is changed to benzimidazolyl. It is a substituted substituent, and at least one hydrogen in the benzimidazole derivative may be substituted with fluorene.

R ¹¹ in the benzoimidazolyl is a hydrogen, an alkyl having 1 to 24 carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, or an aryl having 6 to 30 carbon atoms, and is the above formula (ETM-2-1) and the formula (ETM-). It may be cited to the description of ^{R 11} in 2-2).

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ¹¹ to R ¹⁸ in the formula, the description in the above formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but when these are replaced with benzoimidazole-based substituents, both are used. The pyridine-based substituent may be replaced with a benzoimidazole-based substituent (that is, n = 2), any one of the pyridine-based substituents may be replaced with a benzoimidazole-based substituent, and the other pyridine-based substituent may be replaced with R ^11. It may be replaced with ~ R ¹⁸ (that is, n = 1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole-based substituent, and the “pyridine-based substituent” may be replaced with R ¹¹ to R ¹⁸ .

Specific examples of this benzoimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (10-). Naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4) -(10- (Naphthalen-2-yl) anthracene-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalen-2-yl)) Anthracene-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1-(4- (9,10-di (naphthalen-2-yl) anthracene-2-yl) phenyl) -2- Examples thereof include phenyl-1H-benzo [d] imidazole and 5- (9,10-di (naphthalen-2-yl) anthracene-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole.

This benzimidazole derivative can be produced using a known raw material and a known synthetic method.

<Phenanthroline derivative>
The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006/021982.

R ¹¹ to R ¹⁸ of each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon). The number 6 to 30 aryl). Further, in the above formula (ETM-12-1), any one of R ¹¹ to R ¹⁸ is bonded to φ which is an aryl ring.

At least one hydrogen in each phenanthroline derivative may be replaced with deuterium.

Alkyl in R ¹¹ ~ ^{R 18,} cycloalkyl and aryl may be cited to the description of ^R 11 ^{~ R 18} in the formula (ETM-2). Further, for φ, in addition to the above-mentioned example, for example, the following structural formula can be mentioned. In addition, R in the following structural formula is hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl independently, and * represents a bond position.

Specific examples of this phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-). Phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9' -Difluol-bis (1,10-phenanthroline-5-yl), vasocproin and 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene can be mentioned.

This phenanthroline derivative can be produced using a known raw material and a known synthetic method.

<Kinolinol-based metal complex>
The quinolinol-based metal complex is, for example, a compound represented by the following formula (ETM-13).

In the formula, R ¹ to R ⁶ are hydrogens or substituents, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, and tris (3). , 4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) ( Phenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenorate) aluminum, bis (2-methyl-8- Kinolinolate) (4-methylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-Methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,3-dimethylphenorate) aluminum, bis (2-methyl-8-quinolinolate) ( 2,6-Dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,4-dimethylphenorate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-di-t-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) Aluminum, bis ( 2-Methyl-8-quinolinolate) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl -8-quinolinolate) (2,4,5,6-tetramethylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2) -Naftrat) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) Aluminum, bis (2,4-dimethyl-8-quinolinolate) G) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethyl) Phenolate) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis ( 2-Methyl-8-quinolinolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-4-) Ethyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolate) 2-Methyl-4-methoxy-8-quinolinolate) aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, Bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum, bis (10-hydroxybenzo [h] quinolinate) ) Berylium and the like.

This quinolinol-based metal complex can be produced by using a known raw material and a known synthesis method.

<Reducing substance>
At least one of the electron transport layer and the electron injection layer may contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances are used as long as they have a certain reducing property. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali. From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2.95 eV). Alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV) are mentioned, and those having a work function of 2.9 eV or less are particularly preferable. Of these, the more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more kinds of alkali metals is also preferable, and in particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be improved.

2-1-4. The cathode and cathode 108 in the organic electroluminescent device plays a role of injecting electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material for forming the cathode 108 is not particularly limited as long as it is a substance capable of efficiently injecting electrons into the organic layer, but a material similar to the material for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloy, magnesium). -Indium alloy, aluminum-lithium alloy such as lithium fluoride / aluminum, etc.) are preferable. Alloys containing lithium, sodium, potassium, cesium, calcium, magnesium or these low work function metals are effective for increasing electron injection efficiency and improving device characteristics. However, these low work function metals are generally often unstable in the atmosphere. In order to improve this point, for example, a method of doping an organic layer with a trace amount of lithium, cesium or magnesium and using a highly stable electrode is known. Inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used as other dopants. However, it is not limited to these.

In addition, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium for electrode protection, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride. , Laminating a hydrocarbon-based polymer compound or the like is given as a preferable example. The method for producing these electrodes is also not particularly limited as long as conduction can be obtained, such as resistance heating, electron beam deposition, sputtering, ion plating and coating.

2-1-5. Hole injection layer and hole transport layer in the organic electroluminescent device The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. It will be fulfilled. The hole transport layer 104 plays a role of efficiently transporting the holes injected from the anode 102 or the holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more of the hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder, respectively. Will be done. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

As a hole injection / transporting substance, it is necessary to efficiently inject / transport holes from the positive electrode between electrodes to which an electric field is applied, and the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. For that purpose, it is preferable that the substance has a small ionization potential, a large hole mobility, excellent stability, and is less likely to generate trap impurities during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a hole charge transport material, a p-type semiconductor, and a hole injection of an organic electroluminescent device are used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), and triarylamine derivatives (aromatic tertiary). Polymers with amino in the main or side chains, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl -N, ^{N'-diphenyl-4,4'-diphenyl-1,1'-diamine, N} 4, N ^{4 '-} diphenyl - N ^{^4,} N ⁴ ^'- bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] ^{^{-4,4'-diamine, N 4, N 4, N}} 4', N 4 ^' -Tetra [1,1'-biphenyl] -4-yl)-[1,1'-biphenyl] -4,4'-diamine, 4,4', 4 "-tris (3-methylphenyl (phenyl) Triphenylamine derivatives such as amino) triphenylamine, starburstamine derivatives, etc.), stillben derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives , Kinoxalin derivatives (eg, 1,4,5,8,9,12-hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivatives having the monomer in the side chain, polyvinylcarbazole, polysilane, etc. are preferable, but a thin film necessary for producing a light emitting element can be formed and holes can be injected from the anode. Further, the compound is not particularly limited as long as it can transport holes.

It is also known that the conductivity of organic semiconductors is strongly affected by its doping. Such an organic semiconductor matrix substance is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping electron donors. (For example, the document "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (22), 3202-3204 (1998)" and the document "J. Blochwitz, M." .Pfeiffer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (6), 729-731 (1998) "). They generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number of holes and the mobility, the conductivity of the base material changes considerably. As the matrix substance having hole transporting properties, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA or the like) or a specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc or the like) is known (Japanese Patent Laid-Open No. 2005-167 No. 175).

2-1-6. The anode- anode 102 in the organic electroluminescent device serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these. ..

Examples of the material forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxidation, etc.). (IZO, etc.), metals halide (copper iodide, etc.), copper sulfide, carbon black, ITO glass, nesa glass, etc. Examples of the organic compound include polythiophene such as poly (3-methylthiophene) and conductive polymers such as polypyrrole and polyaniline. In addition, it can be appropriately selected and used from the substances used as the anode of the organic electroluminescent device.

The resistance of the transparent electrode is not limited as long as a sufficient current can be supplied to emit light from the light emitting element, but it is desirable that the resistance is low from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω / □ or less functions as an element electrode, but since it is now possible to supply a substrate of about 10 Ω / □, for example, 100 to 5 Ω / □, preferably 50 to 5 Ω. It is especially desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used in the range of 50 to 300 nm.

2-1-7. The substrate 101 in the organic electroluminescent element serves as a support for the organic electroluminescent element 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. As for the glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness may be sufficient to maintain the mechanical strength. Therefore, for example, 0.2 mm or more may be used. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. As for the material of the glass, non-alkali glass is preferable because it is better that there are few elution ions from the glass, but soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so this can be used. it can. Further, in order to enhance the gas barrier property, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side, and a synthetic resin plate, film or sheet having a particularly low gas barrier property may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

2-1-8. Electron blocking layer in an organic electroluminescent device An electron blocking layer that prevents diffusion of electrons and / or excitons from the light emitting layer may be provided between the hole injection / transport layer and the light emitting layer. A compound represented by any of the above formulas (H1), (H2) and (H3) can be used for forming the electron blocking layer.

2-1-9. Method for manufacturing organic electroluminescent device For each layer constituting the organic electroluminescent device, the material to be formed of each layer is deposited by a vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method. , It can be formed by forming a thin film by a method such as a coating method. The film thickness of each layer formed in this manner is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed by using a thin film deposition method, the vapor deposition conditions differ depending on the type of material, the target crystal structure and association structure of the film, and the like. The vapor deposition conditions are generally: heating temperature of the crucible for vapor deposition + 50 to + 400 ° C., vacuum degree ^10-6 to 10 ^-3 Pa, vapor deposition rate 0.01 to 50 nm / sec, substrate temperature -150 to + 300 ° C., film thickness 2 nm. It is preferable to set it appropriately in the range of about 5 μm.

Next, as an example of a method for producing an organic electroluminescent device, a light emitting layer / electron transport layer containing an anode / hole injection layer / hole transport layer / host compound, a thermoactive delayed phosphor, and a compound having a boron atom. A method for manufacturing an organic electroluminescent device composed of an electron injection layer / a cathode will be described.

2-1-9-1. The deposition suitable substrate, after forming a thin film of an anode material is formed by a vapor deposition method or the like anode, to form a thin film of the hole injection layer and a hole transport layer on the anode. A host compound, a thermoactive delayed phosphor, and a compound having a boron atom are co-deposited on the host compound to form a thin film to form a light emitting layer, and an electron transport layer and an electron injection layer are formed on the light emitting layer. A desired organic electroluminescent element can be obtained by forming a thin film made of a material for a cathode by a vapor deposition method or the like to form a cathode. In the above-mentioned production of the organic electroluminescent device, the production order may be reversed, and the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be manufactured in this order. It is possible.

2-1-9-2. Wet film formation method In the case of a composition for forming a light emitting layer, a film is formed by using a wet film formation method.

In the wet film forming method, a coating film is generally formed by a coating step of applying a light emitting layer forming composition to a substrate and a drying step of removing a solvent from the applied light emitting layer forming composition. Depending on the difference in the coating process, the method using a spin coater is the spin coating method, the method using a slit coater is the slit coating method, the method using a plate is gravure, offset, reverse offset, flexographic printing method, and the method using an inkjet printer is the inkjet method. , The method of spraying in a mist form is called the spray method. The drying step includes methods such as air drying, heating, and vacuum drying. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, different methods may be used in combination, for example, firing under reduced pressure.
That is, the organic electroluminescent device of the present invention has a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and formed from the composition for forming a light emitting layer of the present invention. It is also preferable that it is an electroluminescent element.

The wet film forming method is a film forming method using a solution, and is, for example, a partial printing method (injection method), a spin coating method or a casting method, a coating method, or the like. Unlike the vacuum vapor deposition method, the wet film deposition method does not require the use of an expensive vacuum vapor deposition apparatus and can form a film under atmospheric pressure. In addition, the wet film formation method enables a large area and continuous production, leading to a reduction in manufacturing cost.

On the other hand, when compared with the vacuum vapor deposition method, the wet film deposition method is difficult to stack. When the laminated film is prepared by the wet film forming method, it is necessary to prevent the lower layer from being dissolved by the upper layer composition, and the composition with controlled solubility, the lower layer cross-linking and the orthogonal solvent (Orthogonal solvent) are dissolved in each other. No solvent) etc. are used. However, even if these techniques are used, it may be difficult to use the wet film forming method for coating all the films.

Therefore, in general, a method is adopted in which only some layers are formed by a wet film forming method and the rest are formed by a vacuum vapor deposition method to produce an organic EL element.

For example, the procedure for manufacturing an organic EL device by partially applying the wet film forming method is shown below.
(Procedure 1) Film formation by vacuum deposition method of anode (Procedure 2) Film formation by wet film formation method of hole injection layer (Procedure 3) Film formation by wet film formation method of hole transport layer (Procedure 4) Host compound , A composition for forming a light emitting layer containing a thermoactive delayed phosphor and a compound having a boron atom by a wet film forming method (Procedure 5) A film forming by a vacuum deposition method of an electron transport layer (Procedure 6) An electron injection layer Film formation by vacuum vapor deposition method (Procedure 7) Film formation by vacuum vapor deposition method of cathode By going through this procedure, an anode / hole injection layer / hole transport layer / light emitting layer composed of host material and dopant material / electron transport An organic EL element including a layer / electron injection layer / cathode can be obtained.

2-1-9-3. Organic solvent The compound of the present invention can be dissolved in a solvent and used as a composition for forming a light emitting layer.
The composition for forming a light emitting layer of the present invention contains at least one compound of the present invention and a solvent.
Further, the composition for forming a light emitting layer of the present invention contains at least one compound represented by the above formulas (H1) to (H5), or has a structure represented by the above formulas (H1) to (H5). It is preferable to contain at least one polymer compound having at least one as a repeating unit.
Further, the composition for forming a light emitting layer of the present invention may further contain other components such as an emerging dopant and an assistant dopant used as additional components of the light emitting layer.
For example, the composition for forming a light emitting layer of the present invention preferably contains at least one compound represented by any of the above formulas (AD1), (AD2) and (AD3).
The composition for forming a light emitting layer of the present invention preferably contains at least one organic solvent as the solvent. By controlling the evaporation rate of the organic solvent at the time of film formation, it is possible to control and improve the film forming property, the presence or absence of defects in the coating film, the surface roughness, and the smoothness. Further, when the film is formed by using the inkjet method, the meniscus stability at the pinhole of the inkjet head can be controlled, and the ejection property can be controlled and improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and life of the organic EL device having the light emitting layer obtained from the light emitting layer forming composition can be improved. Can be done.

(Physical properties of organic solvent)
The composition for forming a light emitting layer of the present invention preferably contains an organic solvent having a boiling point of 130 ° C. or higher, more preferably 140 ° C. or higher, and an organic solvent having a boiling point of 150 ° C. or higher. It is more preferable to contain a solvent. The upper limit of the boiling point of the organic solvent is preferably 300 ° C. or lower, more preferably 270 ° C. or lower, and even more preferably 250 ° C. or lower. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of ejection property of the inkjet. Further, when the boiling point is lower than 300 ° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent and smoothness. The solvent is more preferably composed of two or more kinds of organic solvents from the viewpoint of good inkjet ejection property, film forming property, smoothness and low residual solvent. On the other hand, in some cases, the composition may be in a solid state by removing the solvent from the composition for forming a light emitting layer in consideration of transportability and the like.

The solvent is a mixed solvent containing a good solvent (GS) and a poor solvent (PS) for at least one of the compounds of the present invention, and the boiling point (BP _GS ) of the good solvent ( _GS ) is the poor solvent (PS). It is preferably lower than the boiling point (BP _PS ) of.
By adding the poor solvent having a high boiling point, the good solvent having a low boiling point volatilizes first at the time of film formation, and the concentration of the content in the composition and the concentration of the poor solvent increase, and rapid film formation is promoted. As a result, a coating film having few defects, a small surface roughness, and high smoothness can be obtained.
Difference between at least one solubility ( _SGS ,%) of the compound of the present invention in a good solvent (GS) and at least one solubility ( _SPS ,%) of the compound of the present invention in a poor solvent (PS) ( _SGS- S _PS ) is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more.
The above difference in good boiling point of the solvent boiling point _{(GS) (BP} GS) and poor solvent _{_{(PS) (BP PS) (}} BP PS -BP GS) is preferably 10 ° C. or more, at 30 ° C. or higher Is more preferable, and more preferably 50 ° C. or higher.

Further, the solvent contains a good solvent (GS) and a poor solvent (PS) for the compound represented by the formula (1), the formula (H1), the formula (H2), the formula (H3) or the formula (H4), and is good. A combination in which the boiling point (BP _GS ) of the solvent ( _GS ) is lower than the boiling point (BP _PS ) of the poor solvent (PS) is particularly preferable.
By adding the poor solvent having a high boiling point, the good solvent having a low boiling point volatilizes first at the time of film formation, and the concentration of the content in the composition and the concentration of the poor solvent increase, and rapid film formation is promoted. As a result, a coating film having few defects, a small surface roughness, and high smoothness can be obtained.

Good solvent equation for (GS) (1), and the formula (H1), the formula (H2), the formula (H3), the formula (H4) or solubility of the compounds of the formula _{(H5) (S GS),} a poor solvent equation for (PS) (1), the formula (H1), the formula (H2), the formula (H3), the difference of formula (H4) or solubility of the compounds of the formula _{_{(H5) (S PS) (}} S GS - S _PS ) is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more. The difference in boiling points (BP _PS- BP _GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably 50 ° C. or higher.

The organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, and heating after the film formation. When heating is performed, it is preferable to perform it at the glass transition temperature (Tg) of the first component + 30 ° C. or lower from the viewpoint of improving the coating film forming property. From the viewpoint of reducing the residual solvent, it is preferable to heat the first component at the glass transition point (Tg) of −30 ° C. or higher. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(Specific example of organic solvent)
Examples of the organic solvent used in the composition for forming a light emitting layer include an alkylbenzene solvent, a phenyl ether solvent, an alkyl ether solvent, a cyclic ketone solvent, an aliphatic ketone solvent, a monocyclic ketone solvent, and a diester skeleton. Examples thereof include solvents and fluorine-containing solvents, and specific examples thereof include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, heptane-2-ol, and octane-. 2-ol, decane-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Acetate, Diethylene glycol dimethyl ether, Dipropylene glycol dimethyl ether, Diethylene glycol ethyl methyl ether, Diethylene glycol isopropyl methyl ether, Dipropylene glycol monomethyl ether, Diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol butyl methyl ether, Tripropylene glycol dimethyl ether, Triethylene glycol dimethyl ether, Diethylene glycol Monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene, o-xylene, 2,6 -Lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3- Dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, xylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methylanisole, phenetol, benzodioxol , 4-Methylanisole, s-butylbenzene, 3-Methylanisole, 4-Fluoro-3-methylanisole, Xylene, 1, 2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decahydronaphthalene) , Neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3,4-Dimethylanisole, o-tolunitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, Butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-vitryl, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1-methyl- 4- (Propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) benzene, 1-methyl -4- (Heptyloxymethyl) benzenebenzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether and the like, but are not limited thereto. Moreover, the solvent may be used alone or may be mixed.

2-1-10. Application Examples of Organic Electroluminescent Devices The present invention can also be applied to display devices provided with organic electroluminescent devices, lighting devices provided with organic electroluminescent devices, and the like.
The display device of the present invention includes the organic electroluminescent device of the present invention. Further, the lighting device of the present invention includes the organic electroluminescent element of the present invention.
A display device or a lighting device provided with an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment to a known driving device, and can be manufactured by a known method such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescent (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). (See Japanese Patent Application Laid-Open No. 2004-281806, etc.). In addition, examples of the display method of the display include a matrix and / or segment method. The matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are arranged two-dimensionally such as in a grid pattern or mosaic pattern, and characters and images are displayed as a set of pixels. The shape and size of the pixels are determined by the application. For example, for displaying images and characters on a personal computer, monitor, or television, quadrangular pixels with a side of 300 μm or less are usually used, and in the case of a large display such as a display panel, pixels with a side on the order of mm should be used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. Then, as the driving method of this matrix, either a line sequential driving method or an active matrix may be used. Line sequential drive has the advantage of a simpler structure, but when considering operating characteristics, the active matrix may be superior, so it is also necessary to use it properly depending on the application.

In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined area is made to emit light. For example, time and temperature displays on digital clocks and thermometers, operating status displays of audio equipment and electromagnetic cookers, and panel displays of automobiles can be mentioned.

Examples of the lighting device include a lighting device such as an indoor lighting device, a backlight of a liquid crystal display device, and the like (for example, JP-A-2003-257621, JP-A-2003-277741, JP-A-2004-119211). Etc.). The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light by itself, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, as a backlight for a liquid crystal display device, especially for a personal computer for which thinning is an issue, considering that it is difficult to thin the backlight because the conventional method consists of a fluorescent lamp and a light guide plate, the present embodiment The backlight using the light emitting element according to the above is characterized by being thin and lightweight.

2-2. Other Organic Devices The compounds of the present invention can be used in the production of organic field effect transistors, organic thin-film solar cells, and the like, in addition to the organic electroluminescent devices described above. In the organic field effect transistor, the compound of the present invention is preferably used in the active layer. It is preferable that the compound of the present invention is used in the active layer in an organic thin film solar cell.

The organic field effect transistor is a transistor that controls the current by the electric field generated by the voltage input, and is provided with a gate electrode in addition to the source electrode and drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. The field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.

The structure of an organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with an organic semiconductor active layer formed by using the compound of the present invention, and an insulating layer (dielectric) in contact with the organic semiconductor active layer. It suffices if the gate electrode is provided across the body layer). Examples of the element structure include the following structures.
(1) Substrate / Gate electrode / Insulator layer / Source electrode / Drain electrode / Organic semiconductor active layer (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode / Drain electrode (3) Substrate / Organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) Substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode The organic electric field effect transistor configured in this way is It can be applied as a pixel-driven switching element of an active matrix-driven liquid crystal display or an organic electroluminescence display.

The organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The compound of the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties. The compound of the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. In addition to the above, the organic thin film solar cell may appropriately include a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like. For the organic thin-film solar cell, known materials used for the organic thin-film solar cell can be appropriately selected and used in combination.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Examples of synthesis of the compounds used in the examples are shown below.
<Evaluation method of basic physical properties>
Preparation of sample When evaluating the absorption characteristics and emission characteristics (fluorescence and phosphorescence) of the compound to be evaluated, there are cases where the compound to be evaluated is dissolved in a solvent and evaluated in the solvent, and cases where the evaluation is performed in a thin film state. Further, when evaluating in a thin film state, depending on the mode of use of the compound to be evaluated in the organic EL element, only the compound to be evaluated is thinned and evaluated, and the compound to be evaluated is dispersed in an appropriate matrix material. It may be thinned and evaluated. Here, a thin film obtained by depositing only the compound to be evaluated is referred to as a "single film", and a thin film obtained by applying a coating liquid containing the compound to be evaluated and a matrix material and drying the film is referred to as a "coating film".

As the matrix material, commercially available PMMA (polymethylmethacrylate) or the like can be used. In this example, PMMA and the compound to be evaluated are dissolved in toluene, and then a thin film is formed on a transparent support substrate (10 mm × 10 mm) made of quartz by a spin coating method to prepare a sample.

Further, a thin film sample when the matrix material is a host compound is prepared as follows.
A transparent quartz support substrate (10 mm x 10 mm x 1.0 mm) is fixed to a substrate holder of a commercially available vapor deposition equipment (manufactured by Choshu Sangyo Co., Ltd.), and a molybdenum vapor deposition boat containing a host compound and a dopant material are inserted. After installing the molybdenum vapor deposition boat, the vacuum chamber is depressurized to 5 × 10 ^-4 Pa. Next, the vapor deposition boat containing the host compound and the vapor deposition boat containing the dopant material are heated at the same time, and the host compound and the dopant material are co-deposited to an appropriate thickness to obtain the host compound and the dopant material. A mixed thin film (sample) was formed. Here, the vapor deposition rate is controlled according to the set mass ratio of the host compound and the dopant material.

Evaluation of Absorption Characteristics and Emission Characteristics The absorption spectrum of the sample is measured using an ultraviolet-visible near-infrared spectrophotometer (Shimadzu Corporation, UV-2600). The fluorescence spectrum or phosphorescence spectrum of the sample is measured using a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation).

For measurement of fluorescence spectrum, excite at room temperature with an appropriate excitation wavelength and measure photoluminescence. For the measurement of the phosphorescence spectrum, the sample is measured in a state of being immersed in liquid nitrogen (temperature 77K) using an attached cooling unit. In order to observe the phosphorescence spectrum, an optical chopper was used to adjust the delay time from the excitation light irradiation to the start of measurement. The sample is excited at an appropriate excitation wavelength and photoluminescence is measured.

In addition, the fluorescence quantum yield (PLQY) is measured using an absolute PL quantum yield measuring device (C9920-02G, manufactured by Hamamatsu Photonics Co., Ltd.).

Evaluation of Fluorescence Life (Delayed Fluorescence) The fluorescence life was measured at 300 K using a fluorescence life measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C11367-01). Specifically, the emission component having a fast fluorescence lifetime and the emission component having a slow fluorescence lifetime were observed at the maximum emission wavelength measured at an appropriate excitation wavelength. In the fluorescence lifetime measurement of a general organic EL material that emits fluorescence at room temperature, slow emission components involving the triplet component derived from phosphorescence are rarely observed due to the deactivation of the triplet component due to heat. Absent. When a slow emission component is observed in the compound to be evaluated, it indicates that the triplet energy having a long excitation lifetime is transferred to the singlet energy by thermal activation and observed as delayed fluorescence.

Calculation of energy gap (Eg) Eg = 1240 / A is calculated from the long wavelength end A (nm) of the absorption spectrum obtained by the above method.

Measurement of ionization potential (Ip) A transparent support substrate (28 mm x 26 mm x 0.7 mm) on which ITO (indium tin oxide) is deposited is fixed to a substrate holder of a commercially available thin-film deposition device (manufactured by Choshu Sangyo Co., Ltd.). After mounting the molybdenum vapor deposition boat containing the target compound, the vacuum chamber is depressurized to 5 × 10 ^-4 Pa. Next, the vapor deposition boat is heated to evaporate the target compound to form a single film (Neat film) of the target compound.

Using the obtained single membrane as a sample, the ionization potential of the target compound is measured using a photoelectron spectrometer (Sumitomo Heavy Industries, Ltd. PYS-201).

Calculation of electron affinity (Ea) The electron affinity can be estimated from the difference between the ionization potential measured by the above method and the energy gap calculated by the above method.

Measurement of excited single-term energy level E (S, Sh) and excited triple-term energy level E (T, Sh) For a single film of the target compound formed on a glass substrate, the fluorescence peak of the absorption spectrum is heavy at 77K. The fluorescence spectrum is observed with the peak on the long wavelength side as the excitation light to the extent that it does not become, and the excitation single-term energy level E (S, Sh) is obtained from the shoulder on the short wavelength side of the peak of the fluorescence spectrum.
Further, on a single film of the target compound formed on the glass substrate, a phosphorescence spectrum was observed at 77K with a peak on the long wavelength side as nm excitation light so that the fluorescence peaks of the absorption spectrum did not overlap, and the peak short of the phosphorescence spectrum was observed. The excited triple term energy level E (T, Sh) is obtained from the shoulder on the wavelength side.

<Evaluation of organic EL elements>
As described above, the compounds of the invention, applied to the appropriate energy gap (Eg), because it has as a feature a high triplet excitation energy (E _T) and small DerutaEST, for example, a light emitting layer and a charge transport layer Can be expected, and in particular, application to the light emitting layer can be expected.

Evaluation items and evaluation methods The evaluation items include drive voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), maximum wavelength (nm) of emission spectrum, and full width at half maximum ( nm) and so on. For these evaluation items, values at an appropriate emission brightness can be used.

The quantum efficiency of the light emitting element includes the internal quantum efficiency and the external quantum efficiency. In the internal quantum efficiency, the external energy injected as electrons (or holes) into the light emitting layer of the light emitting element is converted into pure photons. Shows the ratio. On the other hand, the external quantum efficiency is calculated based on the amount of these photons emitted to the outside of the light emitting element, and a part of the photons generated in the light emitting layer is continuously absorbed or reflected inside the light emitting element. Therefore, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.

The measurement method of spectral radiance (emission spectrum) and external quantum efficiency is as follows. Using a voltage / current generator R6144 manufactured by Advantest, the element was made to emit light by applying a voltage. The spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface using a spectroradiance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a completely diffused surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons was integrated over the entire observed wavelength region to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency. The full width at half maximum of the emission spectrum is obtained as the width between the upper and lower wavelengths at which the intensity becomes 50% centering on the maximum emission wavelength.

[1] Fabrication and evaluation of organic EL device In this example, an organic EL device was manufactured according to the structure described in Adv. Mater. 2016, 28, 2777-2781. Table 1 shows the layer structure of the produced organic EL element.

In Table 1, "NPD" is N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, and "TcTa" is 4,4', 4 "-tris (N-carbazolyl). It is a triphenylamine, "mCP" is 1,3-bis (N-carbazolyl) benzene, "mCBP" is 3,3'-bis (N-carbazolyl) -1,1'-biphenyl, and " "BPy-TP2" is 2,7-di ([2,2'-bipyridine] -5-yl) triphenylene, "2CzBN" is 3,4-dicarbazolylbenzonitrile, and (DOBNA1) is 3,11-di. -O-trill-5,9-dioxa-13b-boranaft [3,2,1-de] anthracene.

Example 1: Fabrication and evaluation of device 1 using compound (1-2) as a dopant A glass substrate (26 mm × 28 mm × 0.7 mm) on which an anode made of ITO (indium tin oxide) having a thickness of 50 nm is formed. ), Each thin film is laminated with a vacuum degree of 5 × 10 ^-4 Pa by a vacuum vapor deposition method.
First, NPD is deposited on ITO so as to have a film thickness of 40 nm, and TcTa is deposited on ITO so as to have a film thickness of 15 nm to form a hole injection transport layer composed of two layers. Subsequently, mCP is vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, the compound mCBP as a host and the compound (1-2) as a dopant are co-deposited from different vapor deposition sources to form a light emitting layer having a film thickness of 20 nm. At this time, the mass ratio of the host, the assisting dopant, and the emerging dopant is 90:10. Next, 2CzBN is deposited to have a film thickness of 10 nm, and then BPy-TP2 is vapor-deposited to a film thickness of 20 nm to form an electron transport layer. Subsequently, LiF is vapor-deposited to a film thickness of 1 nm, and aluminum is vapor-deposited onto the LiF to a film thickness of 100 nm to form a cathode to obtain an organic EL element.

Example 2: Fabrication and evaluation of an element using compound (4-1) as a dopant and DOBNA1 as a host Example except that compound (1-2) is changed to compound (4-1) and mCBP is changed to DOBNA1. An EL element can be obtained by the same procedure and configuration as in 1.

Example 3: Fabrication and evaluation of a device using compound (4-4) as a dopant EL in the same procedure and configuration as in Example 2 except that compound (4-1) is changed to compound (4-4). The element can be obtained.

Example 4: Fabrication and evaluation of a device using compound (4-10) as a dopant EL in the same procedure and configuration as in Example 2 except that compound (4-1) is changed to compound (4-10). The element can be obtained.

In Table 2, "TSPO1" is a diphenyl [4- (triphenylsilyl) phenyl] phosphine oxide. The chemical structure is shown below.

<Example 5>
<Structure A: Element in which the host compound is mCBP, the assisting dopant is 2PXZ-TAZ, and the emtiting dopant is compound (1-2)>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm is used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Choshu Sangyo Co., Ltd.), and tantalum containing NPD, TcTa, mCP, mCBP, 2PXZ-TAZ, compound (1-2), and TSPO1 respectively. A boat for vapor deposition made of aluminum nitride and a boat for vapor deposition made of aluminum nitride containing LiF and aluminum are installed.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ^-4 Pa, first the NPD is heated and vapor-deposited to a film thickness of 40 nm, and then TcTa is heated and vapor-deposited to a film thickness of 15 nm to obtain two layers. It forms a hole injection transport layer composed of. Next, the mCP is heated and vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, mCBP as a host, 2PXZ-TAZ as an assisting dopant, and compound (ED1) as an emulating dopant are simultaneously heated and co-deposited to a film thickness of 20 nm to form a light emitting layer. The deposition rate is adjusted so that the mass ratio of the host, assisting dopant, and emerging dopant is approximately 90: 9: 1. Next, TSPO1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate of each of the above layers is 0.01 to 1 nm / sec. Then, LiF is heated and vapor-deposited to a film thickness of 1 nm at a vapor deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. Then, an organic EL element can be obtained. At this time, the vapor deposition rate of aluminum is adjusted to be 1 nm to 10 nm / sec.

<Example 6>
<Structure A: Element in which the host compound is mCBP, the assisting dopant is 2PXZ-TAZ, and the emittering dopant is compound (4-1)>
An EL device can be obtained by the same procedure and configuration as in Example 5 except that the emitting dopant is changed to compound (4-1).

<Example 7>
<Structure A: Element in which the host compound is mCBP, the assisting dopant is compound (1-2), and the emittering dopant is compound (ED1)>
An EL device can be obtained by the same procedure and configuration as in Example 5 except that the assisting dopant is changed to compound (1-2) and the emittering dopant is changed to compound (ED1).

<Example 8>
<Structure A: Element in which the host compound is mCBP, the assisting dopant is compound (1-2), and the emittering dopant is compound (4-1)>
An EL device can be obtained by the same procedure and configuration as in Example 7 except that the assisting dopant is changed to compound (4-1).

Synthesis Example 1: Synthesis of compound (4-4-1)

Under a nitrogen atmosphere, 10H-phenoxazine (0.68 g, 3.7 mmol), sodium-t-butoxide (NaOtBu, 0.45 g, 4.6 mmol), toluene (30 ml), tri-t-butylphosphonium tetrafluoroborate. ([(T-Bu) ₃ PH] BF ₄ , 0.05 g, 0.15 mmol), intermediate A (1.5 g, 1.54 mmol), and bis (dibenzylideneacetone) palladium as a palladium catalyst (Pd (dba) ) 2, 0.04 g, 0.04 mmol) was placed in a flask and heated under heating and reflux for 6 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-4-1) (0.32 g, yield 16%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 2.30 (s, 30H), 5.72 (s, 2H), 5.75 (5.745.745.745.745.745.745.745) .745.745.745.745.745.745.745.745.745.74,2H) 5.84 (s, 1H), 6.82 (d, 2H), 6.94 (d, 4H) , 7.02-7.05 (m, 12H), 7.12-7.14 (m, 6H), 7.33-7.37 (m, 6H), 7.41 (s, 2H), 9 .31 (d, 2H), 10.52 (s, 1H).

Synthesis Example 2: Synthesis of compound (4-10-1)

Under nitrogen atmosphere, 10H-phenothiazine (0.80 g, 4.0 mmol), sodium-t-butoxide (NaOtBu, 0.45 g, 3.0 mmol), toluene (30 ml), tri-t-butylphosphonium tetrafluoroborate ( [(T-Bu) ₃ PH] BF ₄ , 0.04 g, 0.14 mmol), intermediate A (1.5 g, 1.5 mmol), and bis (dibenzylideneacetone) palladium (Pd (dba)) as a palladium catalyst. ₂ , 0.04 g, 0.04 mmol) was placed in a flask and heated under heating and reflux for 3 hours. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-10-1) (0.9 g, 1.5 mmol, yield 45%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 2.27 (s, 30H), 5.71 (s, 2H), 5.75 (s, 2H), 5.86 (s, 1H), 6 .83 (d, 2H), 6.96 (t, 4H), 7.07-7.20 (m, 18H), 7.31 (s, 4H), 7.36 (d, 2H), 7. 43 (s, 2H), 9.31 (d, 2H), 10.52 (s, 1H).

Synthesis Example 3: Synthesis of compound (4-1-1)

Under a nitrogen atmosphere, 9,9-dimethyl-9,10-dihydroaclysine (0.78 g, 3.7 mmol), sodium-t-butylid (NaOtBu, 0.45 g, 4.6 mmol), toluene (30 ml), tri- t-Butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.05 g, 0.15 mmol), intermediate A (1.5 g, 1.54 mmol), and bis (didi) as a palladium catalyst. Benzidyleneacetone) palladium (Pd (dba) ₂ , 0.04 g, 0.039 mmol) was placed in a flask and heated under heating reflux for 5 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-1-1) (0.7 g, yield 35%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.68 (s, 12H), 2.30 (s, 30H), 5.74 (s, 2H), 5.75 (s, 2H), 5 .87 (s, 1H), 6.81 (d, 2H), 6.94 (t, 4H), 7.06 (s, 4H), 7.10 (s, 2H), 7.14-7. 19 (m, 12H), 7.34-7.36 (m, 6H), 7.43 (s, 2H), 9.32 (d, 2H), 10.51 (s, 1H).

Synthesis Example 4: Synthesis of compound (4-94-1)

Under a nitrogen atmosphere, 9,9-dimethyl-9,10-dihydroaclysine (0.87 g, 4.15 mmol), sodium-t-butoxyd (NaOtBu, 0.50 g, 5.2 mmol), toluene (30 ml), tri- t-Butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.05 g), intermediate B (1.5 g, 1.73 mmol), and bis (dibenzylideneacetone) palladium as a palladium catalyst. (Pd (dba) ₂ , 0.04 g, 0.04 mM) was placed in a flask and heated under heating and reflux for 8 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4.94-1) (0.91 g, yield 43%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.69 (s, 12H), 2.29 (s, 24H), 5.72 (s, 2H), 5.73 (s, 2H), 5 .84 (s, 1H), 6.36 (d, 2H), 6.81-6.95 (m, 6H), 7.07 (s, 2H), 7.13-7.36 (m, 18H) ), 7.13 (s, 3H), 7.39 (s, 2H), 9.16 (d, 2H), 10.30 (s, 1H).

Synthesis Example 5: Synthesis of compound (4-2221)

Under a nitrogen atmosphere, 10H-phenothiazine (0.85 g, 4.25 mmol), sodium-t-butoxide (NaOtBu, 0.51 g, 5.3 mmol), toluene (30 ml), tri-t-butylphosphonium tetrafluoroborate ( [(T-Bu) ₃ PH] BF ₄ , 0.05 g, 0.18 mmol), intermediate C (1.5 g, 1.77 mmol), and bis (dibenzylideneacetone) palladium (Pd (dba)) as a palladium catalyst. ₂ , 0.04 g, 0.04 mmol) was placed in a flask and heated under heating and reflux for 10 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-2221) (0.77 g, yield 37%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.26 (s, 18H), 2.28 (s, 12H), 5.71 (s, 2H), 5.73 (s, 2H), 5 .86 (s, 1H), 6.84-7.36 (m, 20H), 7.04 (s, 4H), 7.14 (s, 2H), 9.16 (d, 2H), 10. 32 (s, 1H).

Synthesis Example 6: Synthesis of compound (1-296-1)

Under a nitrogen atmosphere, 10,10-dimethyl-5,10-dihydrodibenzo [b, e] [1,4] azacillin (1.35 g, 6.0 mmol), sodium-t-butoxide (NaOtBu, 1.4 g, 15) .0 mmol), toluene (100 ml), tri-t-butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.15 g, 0.5 mmol), intermediate E (2.81 g, 5) .0 mmol) and bis (dibenzylideneacetone) palladium (Pd (dba) ₂ , 0.11 g, 0.13 mmol) as a palladium catalyst were placed in a flask and heated under reflux under heating for 4 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene / heptane (= 1/9 (volume ratio)) to obtain compound (1-296-1) (2.50 g, yield 53%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 0.65 (s, 12H), 2.20 (s, 12H), 7.04-7.12 (m, 10H), 7.23 (s,, 2H), 7.29-7.41 (m, 12H), 7.40 (s, 2H), 7.71 (d, 2H), 8.70 (d, 2H).

Synthesis Example 7: Synthesis of compound (1-295)

Under a nitrogen atmosphere, 10,10-dimethyl-5,10-dihydrodibenzo [b, e] [1,4] azacillin (1.35 g, 6.0 mmol), sodium-t-butoxide (NaOtBu, 1.4 g, 15) .0 mmol), toluene (100 ml), tri-t-butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.15 g, 0.5 mmol), intermediate E (2.37 g, 5) .0 mmol) and bis (dibenzylideneacetone) palladium (Pd (dba) ₂ , 0.11 g, 0.13 mmol) as a palladium catalyst were placed in a flask and heated under reflux under heating for 4 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene / heptane (= 1/20 (volume ratio)) to obtain compound (1-295) (1.80 g, yield 42%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 0.67 (s, 12H), 1.74-2.01 (m, 15H), 7.04 (t, 4H), 7.21 (s, 2H), 7.28-7.43 (m, 12H), 7.39 (s, 2H), 7.69 (d, 2H), 8.67 (d, 2H).

Synthesis Example 8: Synthesis of compound (2-30)

Under a nitrogen atmosphere, 10,10-dimethyl-5,10-dihydrodibenzo [b, e] [1,4] azacillin (1.35 g, 6.0 mmol), sodium-t-butoxide (NaOtBu, 1.4 g, 15) .0 mmol), toluene (100 ml), tri-t-butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.15 g, 0.5 mmol), intermediate F (2.08 g, 5) .0 mmol) and bis (dibenzylideneacetone) palladium (Pd (dba) ₂ , 0.11 g, 0.13 mmol) as a palladium catalyst were placed in a flask and heated under reflux under heating for 3 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene / heptane (= 1/9 (volume ratio)) to obtain compound (2-30) (1.93 g, yield 64%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 0.64 (s, 6H), 1.25 (s, 18H), 7.02 (t, 2H), 7.24 (s, 2H), 7 .30-7.40 (m, 6H), 7.40 (s, 2H), 7.71 (d, 2H), 8.67 (d, 2H).

Synthesis Example 9: Synthesis of compound (2-26)

Under a nitrogen atmosphere, 10H-phenoxazine (1.10 g, 6.0 mmol), sodium-t-butoxide (NaOtBu, 1.4 g, 15.0 mmol), toluene (100 ml), tri-t-butylphosphonium tetrafluoroborate. ([(T-Bu) ₃ PH] BF ₄ , 0.15 g, 0.5 mmol), intermediate F (2.08 g, 5.0 mmol), and bis (dibenzylideneacetone) palladium as a palladium catalyst (Pd (dba) ) ₂ , 0.11 g, 0.13 mmol) was placed in a flask and heated under reflux under heating for 3 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene / heptane (= 1/5 (volume ratio)) to obtain compound (2-26) (1.44 g, yield 51%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.27 (s, 18H), 6.96-7.00 (m, 6H), 7.15 (d, 2H), 7.21 (s, 2H), 7.40 (s, 2H), 7.71 (d, 2H), 8.69 (d, 2H).

Synthesis Example 10: Synthesis of compound (4-4)

Under nitrogen atmosphere, 10H-phenoxazine (2.20 g, 12.0 mmol), sodium-t-butoxide (NaOtBu, 1.44 g, 15.0 mmol), toluene (150 ml), tri-t-butylphosphonium tetrafluoroborate ([(T-Bu) 3PH] BF4, 0.15 g, 0.50 mmol), intermediate G (4.16 g, 1.54 mmol), and bis (dibenzylideneacetone) palladium (Pd (dba) 2) as a palladium catalyst. , 0.11 g, 0.13 mmol) was placed in a flask and heated under reflux under heating for 8 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-4) (0.83 g, yield 15%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 5.70 (s, 2H), 5.74 (s, 2H), 5.86 (s, 1H), 6.83-7.15 (m, 28H), 7.32-7.45 (m, 14H), 9.29 (d, 2H), 10.30 (s, 1H).

Synthesis Example 11: Synthesis of compound (4-10)

Under a nitrogen atmosphere, 10H-phenothiazine (0.80 g, 4.0 mmol), sodium-t-butoxide (NaOtBu, 0.45 g, 3.0 mmol), toluene (30 ml), tri-t-butylphosphonium tetrafluoroborate ( [(T-Bu) 3PH] BF4, 0.04 g, 0.14 mmol), intermediate A (1.5 g, 1.5 mmol), and bis (dibenzylideneacetone) palladium (Pd (dba) 2, as a palladium catalyst. 0.04 g (0.04 mmol) was placed in a flask and heated under heating and reflux for 3 hours. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-10-1) (0.9 g, 1.5 mmol, yield 45%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 5.73 (s, 2H), 5.74 (s, 2H), 5.87 (s, 1H), 6.81-7.18 (m, 28H), 7.33-7.48 (m, 14H), 9.28 (d, 2H), 10.30 (s, 1H).

Synthesis Example 12: Synthesis of compound (4-1)

Under a nitrogen atmosphere, 9,9-dimethyl-9,10-dihydroaclysine (0.78 g, 3.7 mmol), sodium-t-butylid (NaOtBu, 0.45 g, 4.6 mmol), toluene (30 ml), tri- t-Butylphosphonium tetrafluoroborate ([(t-Bu) 3PH] BF4, 0.05 g, 0.15 mmol), intermediate A (1.5 g, 1.54 mmol), and bis (dibenzylideneacetone) as a palladium catalyst. ) Palladium (Pd (dba) 2, 0.04 g, 0.039 mmol) was placed in a flask and heated under reflux under heating for 5 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-1-1) (0.7 g, yield 35%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.68 (s, 12H), 5.73 (s, 2H), 5.73 (s, 2H), 5.87 (s, 1H), 6 .83-7.45 (m, 42H), 9.32 (d, 2H), 10.30 (s, 1H).

Synthesis Example 13: Synthesis of compound (4-438-1)

Under a nitrogen atmosphere, carbazole (0.62 g, 3.7 mmol), sodium-t-butoxide (NaOtBu, 0.45 g, 4.6 mmol), toluene (30 ml), tri-t-butylphosphonium tetrafluoroborate ([( t-Bu) ₃ PH] BF ₄ , 0.05 g, 0.15 mmol), intermediate A (1.5 g, 1.54 mmol), and bis (dibenzylideneacetone) palladium (Pd (dba) ₂ , as palladium catalyst. 0.04 g (0.039 mmol) was placed in a flask and heated under heating and reflux for 5 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-438-1) (0.5 g, yield 31%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 2.26 (s, 30H), 5.72 (s, 2H), 5.74 (s, 2H), 5.86 (s, 1H), 6 .82 (d, 2H), 7.04 (s, 4H), 7.10 (s, 2H), 7.16 (t, 4H), 7.31-7.37 (m, 10H), 7. 42 (s, 2H), 7.96 (d, 4H), 8.56 (d, 4H), 9.32 (d, 2H), 10.48 (s, 1H)

Synthesis Example 14: Synthesis of compound (4-13-1)

Under a nitrogen atmosphere, 1,3,6,8-tetramethyl-9H-carbazole (0.83 g, 3.7 mmol), sodium-t-butoxide (NaOtBu, 0.45 g, 4.6 mmol), toluene (30 ml), Tri-t-butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ , 0.05 g, 0.15 mmol), intermediate A (1.5 g, 1.54 mmol), and bis as a palladium catalyst. (Dibenzylideneacetone) palladium (Pd (dba) ₂ , 0.04 g, 0.039 mmol) was placed in a flask and heated under heating and reflux for 5 hours.
After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from toluene to obtain compound (4-13-1) (0.3 g, yield 14%).

The structure of the compound obtained by the NMR spectrum was confirmed.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.91 (s, 12H), 2.29 (s, 30H), 2.37 (s, 12H), 5.72 (s, 2H), 5 .74 (s, 2H), 5.84 (s, 1H), 6.84 (d, 2H), 6.86 (s, 4H), 7.04 (s, 4H), 7.13 (s,, 2H), 7.30 (d, 4H), 7.40 (dd, 2H), 7.42 (s, 2H), 8.69 (s, 4H), 9.30 (d, 2H), 10. 50 (s, 1H)

The following compounds were used in the following examples.

Structural calculation example 1: Preparation and evaluation of a dope film using compound (4-4-1) as a dopant Compound DOBNA1 as a host and compound (4-4-1) as a dopant are co-deposited from different vapor deposition sources. A light emitting layer having a film thickness of 60 nm was formed. At this time, the mass ratio of the host and the emitting dopant was 99: 1.

The prepared dope film was measured for fluorescence spectrum at room temperature, fluorescence spectrum at 77K, and phosphorescence spectrum at 77K using a spectrofluorometer (F-7000, manufactured by Hitachi High-Tech Co., Ltd.). The fluorescence spectrum peak wavelength was obtained from the fluorescence spectrum at room temperature, and the lowest excited single term energy (S1) and the lowest excited triple term energy (T1) were obtained from the rise of each peak from the fluorescence spectrum at 77K and the phosphorescence spectrum at 77K.

The fluorescence lifetime of the prepared doping film was measured at 300 K using a fluorescence lifetime measuring device (C11367-01, manufactured by Hamamatsu Photonics Co., Ltd.).

In addition, in order to estimate the partial HOMO energy of the substituent (phenoxazine group) in compound (4-4-1), the structural calculation of N-phenylphenoxazine was performed.

Structural Calculation Example 2: Preparation and Evaluation of Dope Film Using Compound (BD2) as a Dopant A dope film was prepared in the same procedure as in Example 9 except that the compound (BD2) was used as a dopant. In addition, the prepared dope film was used to measure the fluorescence spectrum at room temperature, the fluorescence spectrum at 77K, the phosphorescence spectrum at 77K, and the delayed fluorescence lifetime. In addition, a structural calculation of triphenylamine was performed in order to estimate the partial HOMO energy of the substituent (diphenylamine group) in the compound (BD2).

Structural calculation example 3: Preparation and evaluation of a doped film using compound (4-10-1) as a dopant A doped film was prepared in the same procedure as in Example 9 except that compound (4-10-1) was used as a dopant. Made. In addition, the prepared dope film was used to measure the fluorescence spectrum at room temperature, the fluorescence spectrum at 77K, the phosphorescence spectrum at 77K, and the delayed fluorescence lifetime. In addition, structural calculations of N-phenylphenothiazine were performed in order to estimate the partial HOMO energy of the substituent (phenothiazine group) in compound (4-10-1).

Structural Calculation Example 4: Preparation and Evaluation of Dope Membrane Using Compound (4-1-1) as Dopant A dope film was prepared in the same procedure as in Example 9 except that compound (4-1-1) was used as a dopant. Made. In addition, the prepared dope film was used to measure the fluorescence spectrum at room temperature, the fluorescence spectrum at 77K, the phosphorescence spectrum at 77K, and the delayed fluorescence lifetime. In addition, a structural calculation of N-phenyldimethylacridine was performed in order to estimate the partial HOMO energy of the substituent (dimethylacridine group) in compound (4-1-1).

Structural Calculation Example 5: Preparation and Evaluation of Dope Film Using Compound (BD3) as a Dopant A dope film was prepared in the same procedure as in Example 9 except that the compound (BD3) was used as a dopant. In addition, the prepared dope film was used to measure the fluorescence spectrum at room temperature, the fluorescence spectrum at 77K, the phosphorescence spectrum at 77K, and the delayed fluorescence lifetime. In addition, structural calculations of N-phenylcarbazole were performed to estimate the partial HOMO energy of the substituent (carbazolyl) in compound (BD3).

The evaluation results and calculation results of structural calculation examples 1 to 5 are summarized in Table 3. In addition, a plot of partial HOMO and delayed fluorescence lifetime of substituents is shown in FIG.

Comparing Structural Calculation Examples 1 to 5, all the compounds had a small ΔEST, and the measured delayed fluorescence lifetime of the compound (4-4-1) of the present invention was the highest in TADF. Since the higher-order triplet energy cannot be measured directly, the delayed fluorescence lifetime was plotted against the HOMO obtained from the structurally calculated values of the substituent structure. The compound (4-4-1), which has a shallower HOMO as a substituent than the compound (BD2) of Structural Calculation Example 2, has a small delayed fluorescence lifetime and is a compound (4-4-1) with respect to the compound (BD2). ) Was expected to improve TADF property because the higher triplet energy was appropriately adjusted by selecting an appropriate substituent.

From the above, it was shown that the TADF property can be improved by adjusting the partial energy of the main skeleton and the partial energy of the substituent. That is, if the structure of the main skeleton is different, the partial structure is also different, and Example 9, Comparative Example 1 and Reference Examples 1 to 3 do not indicate the limitation of substituents.

Compounds in which the boron atom and / or nitrogen atom are substituted at the m-position of each other are known to give light emission with a very narrow half width, but the higher triplet energy is adjusted by using an appropriate substituent. Therefore, the TADF property can be improved.

Example 9: Fabrication and evaluation of an element using the compound (4-4-1) as a dopant A glass substrate (26 mm × 28 mm × 0.) In which an anode made of ITO (indium tin oxide) having a thickness of 50 nm is formed. Each thin film was laminated on 7 mm) at a vacuum degree of 5 × 10 ^-4 Pa by a vacuum vapor deposition method.
First, NPD was deposited on ITO so as to have a film thickness of 40 nm, and TcTa was deposited on ITO so as to have a film thickness of 15 nm to form a hole injection transport layer composed of two layers. Subsequently, mCP was vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, the compound DOBNA1 as a host and the compound (4-4-1) as a dopant were co-deposited from different vapor deposition sources to form a light emitting layer having a film thickness of 20 nm. At this time, the mass ratio of the host and the emitting dopant was 99: 1. Next, 2CzBN was vapor-deposited to a film thickness of 10 nm, and then BPy-TP2 was vapor-deposited to a film thickness of 20 nm to form an electron transport layer. Subsequently, LiF was vapor-deposited to a film thickness of 1 nm, and aluminum was vapor-deposited onto the LiF to a film thickness of 100 nm to form a cathode to obtain an organic EL device.

Comparative Example 1: Fabrication and Evaluation of an Element Using Compound (BD2) as a Dopant An EL element was prepared in the same procedure and configuration as in Example 9 except that compound (4-4-1) was changed to compound (BD2). Obtained.

Example 10: Fabrication and evaluation of a device using compound (4-94-1) as a dopant Same as in Example 9 except that compound (4-4-1) is changed to compound (4-94-1). An EL element was obtained by the procedure and configuration.

Example 11: Fabrication and evaluation of an element using the compound (4-2221) as a dopant The same as in Example 9 except that the compound (4-4-1) is changed to the compound (4-2221). An EL element was obtained by the procedure and configuration.

The element manufactured in Examples 9-11 and Comparative Example 1, until the 90 cd / ^{m 2} when is continuously driven at a current density in the element characteristics and LT90 (initial luminance 100 cd / ^{m 2} at 100 cd / ^{m 2} Time) is summarized in Table 4.
Comparing Examples 9 to 11 and Comparative Example 1, the compound of the present invention obtained high efficiency and long life even when the difference in emission wavelength was taken into consideration. Further, when the skeleton is represented by the formula (4), the half width of the emission spectrum is extremely narrow as compared with the compound represented by the formula (1).

Example 12: Fabrication and evaluation of an element using the compound (1-296-1) as a dopant A glass substrate (26 mm × 28 mm × 0.) In which an anode made of ITO (indium tin oxide) having a thickness of 50 nm is formed. Each thin film was laminated on 7 mm) at a vacuum degree of 5 × 10 ^-4 Pa by a vacuum vapor deposition method.
First, NPD was deposited on ITO so as to have a film thickness of 40 nm, and TcTa was deposited on ITO so as to have a film thickness of 15 nm to form a hole injection transport layer composed of two layers. Subsequently, mCP was vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, the compound mCBP as a host and the compound (4-10-1) as a dopant were co-deposited from different vapor deposition sources to form a light emitting layer having a film thickness of 20 nm. At this time, the mass ratio of the host and the emitting dopant was 90:10. Next, 2CzBN was vapor-deposited to a film thickness of 10 nm, and then BPy-TP2 was vapor-deposited to a film thickness of 20 nm to form an electron transport layer. Subsequently, LiF was vapor-deposited to a film thickness of 1 nm, and aluminum was vapor-deposited onto the LiF to a film thickness of 100 nm to form a cathode to obtain an organic EL device.

Example 13: Fabrication and evaluation of a device using compound (1-295) as a dopant The procedure and configuration are the same as those in Example 12 except that compound (1-296-1) is changed to compound (1-295). Obtained an EL element.

Example 14: Fabrication and evaluation of a device using compound (2-30) as a dopant The procedure and configuration are the same as those in Example 12 except that compound (1-296-1) is changed to compound (2-30). Obtained an EL element.

Example 15: Fabrication and evaluation of a device using compound (2-26) as a dopant The procedure and configuration are the same as those in Example 12 except that compound (1-296-1) is changed to compound (2-26). Obtained an EL element.

Comparative Example 2: Fabrication and Evaluation of an Device Using Compound (BD4) as a Dopant An EL device was prepared in the same procedure and configuration as in Example 12 except that compound (1-296-1) was changed to compound (BD4). Obtained.

The element manufactured in Examples 12-15 and Comparative Example 2, until the 90 cd / ^{m 2} when is continuously driven at a current density in the element characteristics and LT90 (initial luminance 100 cd / ^{m 2} at 100 cd / ^{m 2} Time) is summarized in Table 5.
Comparing Examples 12 to 15 and Comparative Example 2, the compound of the present invention obtained high efficiency and long life even when the difference in emission wavelength was taken into consideration.

Example 16: Fabrication and evaluation of an element using the compound (4-438-1) as a dopant A glass substrate (26 mm × 28 mm × 0.) In which an anode made of ITO (indium tin oxide) having a thickness of 50 nm is formed. Each thin film was laminated on 7 mm) at a vacuum degree of 5 × 10 ^-4 Pa by a vacuum vapor deposition method.
First, NPD was deposited on ITO so as to have a film thickness of 40 nm, and TcTa was deposited on ITO so as to have a film thickness of 15 nm to form a hole injection transport layer composed of two layers. Subsequently, mCP was vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, compound DOBNA1 as a host and compound (4-438-1) as a dopant were co-deposited from different vapor deposition sources to form a light emitting layer having a film thickness of 20 nm. At this time, the mass ratio of the host and the emitting dopant was 99: 1. Next, 2CzBN was vapor-deposited to a film thickness of 10 nm, and then BPy-TP2 was vapor-deposited to a film thickness of 20 nm to form an electron transport layer. Subsequently, LiF was vapor-deposited to a film thickness of 1 nm, and aluminum was vapor-deposited onto the LiF to a film thickness of 100 nm to form a cathode to obtain an organic EL device.

Example 17: Fabrication and evaluation of a device using compound (4-13-1) as a dopant Same as in Example 16 except that compound (4-438-1) is changed to compound (4-13-1). An EL element was obtained by the procedure and configuration.

Table (the time until 90 cd / ^{m 2} when is continuously driven at a current density in the initial luminance 100 cd / ^{m 2)} the elements produced in Example 16 and 17, device characteristics and LT90 in 100 cd / ^{m 2} It is summarized in 6.

100 Organic electroluminescent device 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims

A compound having at least one structure represented by the following formula (i);

In formula (i),
Rings A, B and C each independently represent an aromatic ring structure.
At least one ring member atom in at least one of the A ring, the B ring and the C ring is bonded to the partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X 1 and X 2 are independently>O,>S,>N-R',> C (-R') 2 or> Si (-R') 2 , respectively.
In the partial structure (D), Q is a single bond,>O,>S,> C (-R') 2 or> Si (-R') 2 , and the wavy line indicates the bond position.
A ring member atoms contained in the ring member atoms and C ring contained in the B ring is bridged by X 3, a portion of the part and C rings of the ring B and may form a 6-membered ring containing Y, X 3 is any one of>O,>S,>N-R',> C (-R') 2 or> Si (-R') 2 .
R 21 to R 28 in the partial structure (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Diarylboryl (two aryls may be attached via a single bond or a linking group), a substituent that is cyano or halogen, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
The R'in the above-mentioned Si-R',>N-R',> C (-R') 2 and> Si (-R') 2 can be independently hydrogen, aryl, heteroaryl, alkyl or Cycloalkyl,
In the A ring, B ring and C ring in the formula (i), the structure bonded to the ring member atom not bonded to the partial structure (D), X 1 , X 2 , or Y, and R 21 in the partial structure (D). ~ R 28 is not all hydrogen,
At least one hydrogen in the compound having at least one structure represented by the formula (i) may be substituted with cyano, halogen, deuterium, or partial structure (B).

(In the partial structure (B), R 40 and R 41 are each independently alkyl and may be bonded to each other, and the total carbon number of R 40 and R 41 is 2 to 10, and the wavy line portion is It is a binding site with other structures.)
The compound according to claim 1, which is represented by the following formula (1);

In equation (1),
At least one of R 1 to R 11 is a partial structure (D) represented by the formula (D).
Y is B, P, P = O, P = S or Si-R',
X 1 and X 2 are independently>O,>S,>N-R',> C (-R') 2 or> Si (-R') 2 , respectively.
R 1 to R 11 which are not partial structures (D) are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy. Alternatively, it is a substituent that is diarylboryl (two aryls may be bonded via a single bond or a linking group), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
R 7 and R 8 may be crosslinked at> X 3 to form a 6-membered ring containing part of the b ring, part of the c ring and Y, where X 3 is>O,>S,> N-. R',> C (-R') 2 or> Si (-R') 2
The R'in Si-R',>N-R',> C (-R') 2 and> Si (-R') 2 are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. The two R'of each of the> C (-R') 2 and> Si (-R') 2 may be connected.
R 1 to R 11 which are not the partial structure (D) in the formula (1) and R 21 to R 28 in the partial structure (D) are not all hydrogen.
At least one hydrogen in the compound represented by the formula (1) may be substituted with halogen or deuterium.
In equation (1)
At least one selected from the group consisting of R 1 and R 3 is a partial structure (D).
R 1 to R 11 which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryls), diheteroarylaminos (where heteroaryls are heteroaryls with 2-12 carbon atoms), aryl heteroarylaminos (where aryls are aryls with 6-12 carbon atoms and heteroaryls have 2 carbon atoms). It is a substituent that is an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms (which is a heteroaryl of to 12), and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these may be formed and is substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
R 7 and R 8 may be crosslinked with> X 3
R 21 to R 28 in the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 12 carbon atoms). Aryl), diheteroarylamino (where heteroaryl is a heteroaryl having 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is an aryl having 6 to 12 carbon atoms and heteroaryl is an aryl having 2 to 12 carbon atoms). Heteroaryl), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cyano or halogen substituents, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May have been
R'is independently an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms.
The compound according to claim 2.
In equation (1)
R 2 is the partial structure (D).
R 1 to R 11 which are not the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl substituent that is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms without substitution, and among these substituents, adjacent substituents are bonded to each other to form a ring structure. At least one hydrogen in these substituents may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms. May be
Moiety Q is in the structure (D)> C (-R ' ) 2, a partial structure> in (D) C (-R') R in 2 'methyl and the partial structure (D) R 21 ~ R 28 in When is hydrogen, R 6 and R 9 in the formula (1) are independently partial structures (D), hydrogen, or aryls having 6 to 30 carbon atoms, heteroaryls having 2 to 30 carbon atoms, respectively. Diarylamino (where aryl is aryl with 6-12 carbon atoms), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms), Heteroaryl is a substituent that is an alkyl having 2 to 12 carbon atoms, an alkyl having 1 to 3 carbon atoms without substitution, or a cycloalkyl having 3 to 20 carbon atoms. Among these substituents, adjacent substitution groups are used. The groups may be bonded to each other to form a ring structure, and at least one hydrogen in these substituents is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl or carbon having 1 to 12 carbon atoms. It may be substituted with the number 3 to 20 cycloalkyl.
The compound according to claim 2.
In equation (1)
At least one selected from the group consisting of R 4 , R 5 , R 6 , R 9 , R 10 and R 11 is a partial structure (D).
R 1 to R 11 which are not partial structures (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 30 carbon atoms). 12 aryl), diheteroarylamino (where heteroaryl is heteroaryl with 2-12 carbon atoms), aryl heteroarylamino (where aryl is aryl with 6-12 carbon atoms, heteroaryl is hetero-aryl with 2-12 carbon atoms) Aryl), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms, and among these substituents, adjacent substituents may be bonded to each other to form a ring structure. At least one hydrogen in these may be substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms.
R 7 and R 8 may be crosslinked with> X 3
R 21 to R 28 in the partial structure (D) are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, aryl has 6 to 12 carbon atoms). Aryl), diheteroarylamino (where heteroaryl is a heteroaryl having 2 to 12 carbon atoms), aryl heteroarylamino (where aryl is an aryl having 6 to 12 carbon atoms, and heteroaryl is an aryl having 2 to 12 carbon atoms). (12 heteroaryl), alkyl with 1-12 carbon atoms, cycloalkyl with 3-20 carbon atoms, cyano or halogen substituents, of which adjacent substituents are attached to each other. A ring structure may be formed, and at least one hydrogen in these substituents is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms, or an alkyl having 3 to 20 carbon atoms. May be substituted with cycloalkyl
R'is independently an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms.
The compound according to claim 2.
In the formula (1), claims 2 to 5, wherein X 1 and X 2 are independently>O,>S,> C (-R') 2 or> Si (-R') 2 . The compound according to any one item.
The compound according to any one of claims 2 to 6, wherein X 1 and X 2 are both> O in the formula (1).
The compound according to any one of claims 2 to 7, wherein Y is B in the formula (1).
The compound according to any one of claims 2 to 7, wherein Y is P = O or P = S in the formula (1).
The compound according to any one of claims 2 to 7, wherein Y is Si-R'in the formula (1).
The compound according to any one of claims 2 to 10, wherein in the formula (1), R 7 and R 8 are not crosslinked and do not form a ring.
The compound according to any one of claims 2 to 10, wherein in the formula (1), R 7 and R 8 are crosslinked at> X 3 to form a ring.
The compound according to any one of claims 2 to 12, which has one partial structure (D) in the formula (1).
The compound according to any one of claims 1 to 13, wherein Q in the partial structure (D) is> O or> S.
The compound according to any one of claims 1 to 13, wherein Q in the partial structure (D) is> C (-R) 2 or> Si (-R) 2 .
The compound according to claim 2, which is a compound represented by any of the following formulas.

(In the formula, Me represents methyl and tBu represents t-butyl.)
The compound according to claim 1, which is represented by the following formula (ii);

In formula (ii),
Rings a, b, c and d are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted, and two adjacent hydrogens may be substituted. They may be linked by alkyl to form a ring.
Z 1 and Z 2 are independently -CH = or -N =, and the hydrogen at -CH = may be substituted.
X 1 to X 4 are independently O or N-R, and R of the N-R is aryl, heteroaryl or alkyl, respectively.
At least one ring member atom in at least one ring selected from the group consisting of a ring, b ring, c ring, d ring, and a 6-membered ring including Z 1 and Z 2 is bonded to the partial structure (D). And
In the partial structure (D), R 21 to R 28 are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, and adjacent R 21 to R 28 are based on linking groups. It may form a ring,
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') 2 or> Si (-R') 2 , and the above> C (-R') 2 and> Si. (-R') The R'of 2 is an aryl that may be independently linked with hydrogen, alkyl, or R', respectively.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is a single bond, both R 24 and R 28 do not become hydrogen.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X 1 and X 2 do not become O.
The wavy line portion in the partial structure (D) represents the binding site with the structure represented by the formula (ii).
At least one hydrogen in the compound represented by the formula (ii) may be substituted with a halogen, deuterium, or a partial structure (B).
The compound according to claim 17, which is represented by the following formula (4);

In formula (4), R 1 to R 14 are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, respectively. Alternatively, it is a substituent that is a diarylboryl (two aryls may be attached via a single bond or a linking group), and at least one hydrogen in these substituents is substituted with aryl, heteroaryl or alkyl. May be
Adjacent two of R 3 to R 14 may be connected by an alkyl having 2 to 8 carbon atoms to form a ring.
X 1 to X 4 are independently O or N-R, and R of the N-R is an aryl having 6 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, and 1 to 20 carbon atoms. Alkyl or cycloalkyl with 3-8 carbon atoms
At least one of R 1 to R 14 in the formula (4) is a partial structure (D) represented by the formula (D).
In the partial structure (D), R 21 to R 28 are independently hydrogen, aryl, heteroaryl, alkyl, cycloalkyl, cyano, or halogen, respectively.
Adjacent R 21 to R 28 may form a ring with a linking group.
Q in the partial structure (D) is a single bond,>O,>S,> C (-R') 2 or> Si (-R') 2 , and the above> C (-R') 2 and> Si. The R'of (-R') 2 is an independently hydrogen, an alkyl having 1 to 8 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be linked.
When the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is a single bond, both R 24 and R 28 do not become hydrogen.
However, when the partial structure (D) is bonded to only the a ring and the c ring one by one and Q is O, both X 1 and X 2 do not become O.
At least one hydrogen in the compound represented by the formula (4) may be substituted with a halogen, deuterium, or a partial structure (B).
In the formula (4), R 1 to R 14 are independently hydrogen, or aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (where aryl has 6 to 12 carbon atoms). Aryl), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, and aryloxy having 6 to 12 carbon atoms. Alternatively, it is a substituent that is a diallylboryl (where aryl is an aryl having 6 to 12 carbon atoms) (two aryls may be bonded via a single bond or a linking group), and at least one of these substituents. Hydrogen may be substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 8 carbon atoms.
X 1 to X 4 are independently> O or> N-R, and R of> N-R is an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 8 carbon atoms.
In the partial structure (D), R 21 to R 28 are independently hydrogen, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 12 carbon atoms, and 3 to 3 carbon atoms. 20 cycloalkyl, cyano, or halogen, where Q in the partial structure (D) is a single bond,>O,>S,> C (-R') 2 or> Si (-R') 2 . The R'of> C (-R') 2 and> Si (-R') 2 is independently hydrogen or an alkyl having 1 to 8 carbon atoms.
At least one hydrogen in the compound represented by the formula (4) may be substituted with halogen or deuterium.
The compound according to claim 18.
The compound according to claim 18 or 19, wherein in formula (4), one or two of R 4 , R 7 , R 10 and R 13 have a partial structure (D).
The compound according to any one of claims 17 to 20, wherein at least one of R 21 to R 28 is fluorine in the partial structure (D).
The compound according to any one of claims 17 to 21, wherein the partial structure (D) is a structure represented by any of the following formulas (D-1) to (D-3);

In formula (D-1), R 50 independently represents a hydrogen atom or methyl, and Me is methyl.
In formula (D-2), Q 1 represents>O,>S,> C (CH 3 ) 2 , or> Si (CH 3 ) 2 .
The compound according to claim 18, which is represented by any of the following formulas.

(In the formula, Me represents methyl.)
The compound according to any one of claims 17 to 23, which comprises a partial structure (B), a chlorine atom, a bromine atom, or an iodine atom in the structure.
Any of claims 17 to 24, wherein the energy level difference between S1 and T1 is 0.1 eV or less, the energy level difference between S1 and T2 is 0.05 eV or less, and S1 is a locally excited state. The compound according to one item.
The compound according to claim 1, which is a polymer compound having a repeating unit containing a structure represented by the formula (i).
Triarylamine which may have an unsubstituted or substituent, fluorene which may have an unsubstituted or substituent, anthracene which may have an unsubstituted or substituent, and having an unsubstituted or substituent. May be tetracene, triazine which may have an unsubstituted or substituent, carbazole which may have an unsubstituted or substituent, tetraphenylsilane which may have an unsubstituted or substituent, an unsubstituted or substituent. Spirofluorene, which may have a substituent, triphenylphosphine, which may have an unsubstituted or substituent, dibenzothiophene, which may have an unsubstituted or substituent, and an unsubstituted or substituent. The compound according to claim 26, wherein the structure derived from at least one selected from the group consisting of good dibenzofurene is contained in the repeating unit, or in a repeating unit different from the repeating unit.
A material for an organic device containing the compound according to any one of claims 1 to 27.
The material for an organic device according to claim 28, which is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.
The material for an organic device according to claim 29, which is a material for a light emitting layer for an organic electroluminescent element.
An organic electroluminescent device, an organic field effect transistor, or an organic thin-film solar cell containing the compound according to any one of claims 1 to 27.
An organic electroluminescent device including a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and containing the light emitting layer material according to claim 30.
The light emitting layer contains at least one compound represented by the following formula (H1), formula (H2), formula (H3), formula (H4), or formula (H5), or the following (H1), The organic according to claim 32, which contains at least one polymer compound having a structure derived from a compound represented by the formula (H2), the formula (H3), the formula (H4), or the formula (H5) as a repeating unit. Electroluminescent element;

In the formula (H1), L 1 is an arylene having 6 to 24 carbon atoms.
In formula (H2), L 2 and L 3 are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms, respectively.
At least one hydrogen in the compound represented by each of the above formulas may be substituted with alkyl, cyano, halogen or deuterium having 1 to 6 carbon atoms.
In formula (H3), J is>O,>S,>N-R',> C (-R') 2 or> Si (-R') 2 .
Y is a single bond,>O,>S,> C (-R') 2 , or> Si (-R') 2 .
Z is CH, CR'or N,
In formula (H4), Z is CH, CR'or N,
The R'in>N-R',> C (-R') 2 ,> Si (-R') 2 and C-R'are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. Yes,
In formula (H5),
R 1 to R 11 are substituents that are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, and at least one of these substituents. The two hydrogens may be further substituted with aryl, heteroaryl, diarylamino or alkyl,
Adjacent groups of R 1 to R 11 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, in which at least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino or alkyl. Often,
At least one hydrogen in the compound represented by the formula (H5) may be independently substituted with a halogen or deuterium.
The organic electroluminescent device according to claim 32 or 33, which contains at least one compound represented by any of the following formulas (AD1), (AD2) and (AD3);

In formulas (AD1), (AD2) and (AD3),
M is at least one of single bond, -O-,> N-Ar and> CAR 2 independently of each other.
Each of J is independently an arylene having 6 to 18 carbon atoms, and the arylene may be replaced with phenyl, an alkyl having 1 to 6 carbon atoms, and a cycloalkyl having 3 to 12 carbon atoms.
Q is = C (-H)-or = N-, respectively.
Ar is independently hydrogen, an aryl having 6 to 18 carbon atoms, a heteroaryl having 6 to 18 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms, and the aryl and hetero At least one hydrogen in the aryl may be replaced with phenyl, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms.
m is 1 or 2
n is an integer from 2 to (6-m),
At least one hydrogen in the compound represented by each of the above formulas may be substituted with halogen or deuterium.
A composition for forming a light emitting layer, which comprises at least one of the compounds according to any one of claims 1 to 27 and a solvent.
The composition for forming a light emitting layer according to claim 35, which comprises an organic solvent having a boiling point of 150 ° C. or higher as the solvent.
The composition for forming a light emitting layer according to claim 35 or 36, wherein the solvent is a mixed solvent containing a good solvent and a poor solvent for at least one of the compounds, and the boiling point of the good solvent is lower than the boiling point of the poor solvent. Stuff.
It contains at least one compound represented by the formula (H1), the formula (H2), the formula (H3), the formula (H4), or the formula (H5), or the formula (H1), the formula (H2), the formula. (H3), any one of claims 35 to 37, which contains at least one polymer compound having at least one of the structures derived from the compound represented by the formula (H4) or the formula (H5) as a repeating unit. The composition for forming a light emitting layer according to the above section;

In the formula (H1), L 1 is an arylene having 6 to 24 carbon atoms.
In formula (H2), L 2 and L 3 are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms, respectively.
At least one hydrogen in the compound represented by each of the above formulas may be substituted with alkyl, cyano, halogen or deuterium having 1 to 6 carbon atoms.
In formula (H3), J is>O,>S,>N-R',> C (-R') 2 or> Si (-R') 2 .
Y is a single bond,>O,>S,> C (-R') 2 or> Si (-R') 2 .
Z is CH, CR'or N,
In formula (H4), Z is CH, CR'or N,
The R'in>N-R',> C (-R') 2 ,> Si (-R') 2 and C-R'are independently aryl, heteroaryl, alkyl or cycloalkyl, respectively. Yes,
In formula (H5),
R 1 to R 11 are substituents that are independently hydrogen, or aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, and at least one of these substituents. The two hydrogens may be further substituted with aryl, heteroaryl, diarylamino or alkyl,
Adjacent groups of R 1 to R 11 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino or alkyl, in which at least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino or alkyl. Often,
At least one hydrogen in the compound represented by the formula (H1), the formula (H2), the formula (H3), the formula (H4), or the formula (H5) is independently substituted with a halogen or a deuterium. You may.
An organic electroluminescence having a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and formed from the light emitting layer forming composition according to any one of claims 35 to 38. Light emitting element.
It has at least one layer selected from the group consisting of an electron transporting layer and an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane. Selected from the group consisting of derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol metal complexes. The organic electric field light emitting element according to any one of claims 32 to 34 and 39, which comprises at least one of the above.
At least one of the electron transport layer and the electron injection layer is an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal halogen. Claims further comprising at least one selected from the group consisting of compounds, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. 40. The organic electric field light emitting element.
A display device or a lighting device including the organic electroluminescent element according to any one of claims 32 to 34 and 39 to 41.