JP7417221B2 - Polycyclic aromatic compounds - Google Patents

Description

The present invention relates to polycyclic aromatic compounds. The present invention particularly relates to a polycyclic aromatic compound that is a complex containing a coordinate bond between nitrogen and a metal or metalloid, and a polycyclic aromatic compound that is a raw material for producing this complex. The present invention also relates to an organic device material, an organic electroluminescent element, a display device, and a lighting device containing the above complex.

Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied in various ways because they can save power and be made thinner.Furthermore, organic electroluminescent elements made of organic materials can be easily made lighter and larger. As a result, it has been actively considered. In particular, we are developing organic materials that emit light such as blue, which is one of the three primary colors of light, and organic materials that have the ability to transport charges such as holes and electrons (which have the potential to become semiconductors and superconductors). Regarding development, research has been active so far, regardless of whether it is a high-molecular compound or a low-molecular compound.

An organic electroluminescent device has a structure consisting of a pair of electrodes consisting of an anode and a cathode, and one or more layers containing an organic compound and disposed between the pair of electrodes. Layers containing organic compounds include a light-emitting layer and a charge transport/injection layer that transports or injects charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

Among them, Patent Documents 1 and 2 disclose that polycyclic aromatic compounds in which aromatic rings are connected with hetero elements such as boron, phosphorus, oxygen, nitrogen, and sulfur are useful as materials for organic electroluminescent devices, etc. Disclosed. This polycyclic aromatic compound has a large HOMO-LUMO gap, high triplet excitation energy ( _ET ), and exhibits thermally activated delayed fluorescence, so it is said to be particularly useful as a fluorescent material for organic electroluminescent devices. It has been reported.

International Publication No. 2015/102118 Japanese Patent Application Publication No. 2018-43984

As mentioned above, the polycyclic aromatic compounds described in Patent Documents 1 and 2 are useful as fluorescent materials for organic electroluminescent devices, but in order to increase the selection of materials for organic devices such as organic electroluminescent devices, , it is desired to develop materials made of compounds different from conventional ones.

The present inventors have made extensive studies to solve the above problems, and have developed a novel polycyclic aromatic compound in which a metalloid atom or a metal atom such as iridium is coordinately bonded to a nitrogen atom on a polycyclic aromatic compound. They were successful, and after further study, they completed the present invention. That is, the present invention provides the following polycyclic aromatic compounds or multimers thereof, and materials for organic devices containing any of them.

[1] A complex which is a multimer of a polycyclic aromatic compound represented by the following formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following formula (1).

(In formula (1),
Ring A is a heteroaryl ring having at least one nitrogen atom, Ring B and Ring C are each independently an aryl ring or a heteroaryl ring, and Ring A, Ring B, and Ring C are each an aryl ring or a heteroaryl ring. At least one hydrogen of the aryl ring may be substituted,
Y is a metal of Groups 3 to 11 of the periodic table that is coordinated with a ligand, a metal or semimetal of Groups 13 to 14 of the periodic table that is coordinated with a ligand, or a metal that is coordinated with a ligand. Indicates metalloids of Groups 15 and 16 of the periodic table,
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl, or heteroaryl; R may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond,
Z is a carbon atom or a nitrogen atom,
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, halogen, or deuterium. )

[2] The compound according to [1], which is a polycyclic aromatic compound represented by the following formula (1') or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (1') Complex.

(In formula (1'), Z ^a each independently represents C-R ^a or N, or two adjacent Z ^a in the same ring together with the bond between them each represent N- R ^a represents O, S, or Se, and each R ^a is independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino , substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted is cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted silyl, and R ^a substituted on two adjacent Z ^a in the same ring are bonded to each other to form an aryl ring. , a heteroaryl ring, or a cycloalkyl ring, and at least one hydrogen in the formed ring is diarylamino or diarylboryl (even if the two aryls are bonded via a single bond or a linking group). may be replaced with
Y is a metal of Groups 3 to 11 of the periodic table that is coordinated with a ligand, a metal or metalloid of Groups 13 to 14 of the periodic table that is coordinated with a ligand, or a metal that is coordinated with a ligand. Indicates the metalloids of Groups 15 and 16 of the periodic table, which are ranked in
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl, or heteroaryl; R may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond,
Z is a carbon atom or a nitrogen atom,
At least one hydrogen in the compound or structure represented by formula (1') may be substituted with cyano, halogen, or deuterium. )

[3] R ^a is each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, each aryl is aryl having 6 to 12 carbon atoms), or diarylboryl ( However, each aryl is an aryl having 6 to 12 carbon atoms, and two aryls may be bonded via a single bond or a linking group), and two adjacent Z ^a in the same ring are substituted. R ^a may be bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring a, ring b, or ring c, and at least one of the formed rings Two hydrogens are diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms) or diarylboryl (however, each aryl is an aryl having 6 to 12 carbon atoms, and two aryls are connected via a single bond or a linking group). The complex according to [2], which may be substituted with
[4] Y is MR ^x , M is boron or iridium, and R ^x is aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl or sulfonate [1 ] to [3].

（式中、Ｐｈはフェニル、ＯＴｆはトルフルオロメタンスルホナート、Ｃｐ＊はペンタメチルシクロペンタジエニルである。） [5] The complex according to [1], which is represented by any of the following formulas.

(In the formula, Ph is phenyl, OTf is trifluoromethanesulfonate, and Cp* is pentamethylcyclopentadienyl.)

[6] A metal or metalloid complex containing a polycyclic aromatic compound represented by the following formula (11) or a multimer of a polycyclic aromatic compound having multiple structures represented by the following formula (11). Manufacturing raw materials.

(In formula (1),
Ring A is a heteroaryl ring having at least one nitrogen atom, Ring B and Ring C are each independently an aryl ring or a heteroaryl ring, and Ring A, Ring B, and Ring C are each an aryl ring or a heteroaryl ring. At least one hydrogen of the aryl ring may be substituted,
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl, or heteroaryl; R may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11) may be substituted with cyano, halogen, or deuterium. )

[7] A polycyclic aromatic compound represented by formula (11) or a multimer of a polycyclic aromatic compound having multiple structures represented by formula (11) below is represented by formula (11') below. The production raw material according to [6], which is a polycyclic aromatic compound having a structure represented by the following formula (11') or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11').

(In formula (11'), Z ^a each independently represents C-R ^a or N, or two adjacent Z ^a in the same ring together with the bond between them each represent N- R ^a represents O, S or Se, R ^a is each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, Substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted silyl, and R ^a substituted on two adjacent Z ^a in the same ring are bonded to each other to form an aryl ring, A heteroaryl ring or a cycloalkyl ring may be formed, and at least one hydrogen in the formed ring may be diarylamino or diarylboryl (two aryls may be bonded via a single bond or a linking group). ) may be replaced with
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl or heteroaryl; may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11') may be substituted with cyano, halogen, or deuterium. )

[8] In formula (11'),
R ^a is each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms), or diarylboryl (however, each aryl has 6 to 12 carbon atoms). Aryl is an aryl having 6 to 12 carbon atoms, and two aryls may be bonded via a single bond or a linking group), and R ^a substituted on two adjacent Z ^a in the same ring. may be combined with each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring a, ring b, or ring c, and at least one hydrogen in the formed ring is , diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms) or diarylboryl (however, each aryl is an aryl having 6 to 12 carbon atoms, and two aryls are bonded via a single bond or a linking group). ) may be replaced with
The manufacturing raw material according to [7].
[9] The production raw material according to any one of [6] to [8], wherein the complex is the complex according to any one of [1] to [5].

[10] The nitrogen of the A ring of the polycyclic aromatic compound represented by formula (11) or the multimer of the polycyclic aromatic compound having a plurality of structures represented by formula (11), and the nitrogen of ring A of the polycyclic aromatic compound represented by formula (11), and metals of groups 13-14 of the periodic table, or metalloids of groups 15-16 of the periodic table coordinated with a ligand. , a method for producing a complex using the production raw material according to any one of [6] to [8].
[11] The production method according to [10], wherein the complex is the complex according to any one of [1] to [5].

[12] An organic device material containing the complex according to any one of [1] to [5].
[13] An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light-emitting layer disposed between the pair of electrodes and containing the complex according to any one of [1] to [5].
[14] A pair of electrodes consisting of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and a light emitting layer disposed between the cathode and the light emitting layer according to any one of [1] to [5]. An organic electroluminescent device having an electron injection layer and/or an electron transport layer containing a complex.
[15] A pair of electrodes consisting of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and a light emitting layer disposed between the anode and the light emitting layer, according to any one of [1] to [5]. An organic electroluminescent device comprising a hole injection layer and/or a hole transport layer containing a complex of
[16] A display device comprising the organic electroluminescent element according to any one of [13] to [15].
[17] A lighting device comprising the organic electroluminescent element according to any one of [13] to [15].

（式（１１）中、
Ａ環は少なくとも１つの窒素原子を持つヘテロアリール環であり、Ｂ環およびＣ環はそれぞれ独立して、アリール環またはヘテロアリール環であり、Ａ環、Ｂ環およびＣ環それぞれにおけるアリール環またはヘテロアリール環の少なくとも１つの水素は置換されていてもよく、
Ｘ¹、Ｘ²およびＸ³は、それぞれ独立して、Ｏ、Ｎ－Ｒであり、ただし前記Ｎ－ＲのＲはアリールまたはヘテロアリールであり、
Ｚ^XはＣ－ＨまたはＮであり、
式（１１）で表される化合物または構造における少なくとも１つの水素はシアノ、ハロゲンまたは重水素で置換されていてもよい。） [18] A polycyclic aromatic compound represented by the following formula (11), or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11).

(In formula (11),
Ring A is a heteroaryl ring having at least one nitrogen atom, Ring B and Ring C are each independently an aryl ring or a heteroaryl ring, and Ring A, Ring B, and Ring C are each an aryl ring or a heteroaryl ring. At least one hydrogen of the aryl ring may be substituted,
X ¹ , X ² and X ³ are each independently O, NR, provided that R in NR is aryl or heteroaryl,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11) may be substituted with cyano, halogen, or deuterium. )

[19] A polycyclic aromatic compound represented by the following formula (11') or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11').

(In formula (11'), Z ^a each independently represents C-R ^a or N, or two adjacent Z ^a in the same ring together with the bond between them each represent N- R ^a , O, S, or Se; R ^a is each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino , substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted is cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted silyl, and R ^a substituted on two adjacent Z ^a in the same ring are bonded to each other to form an aryl ring. , may form a heteroaryl ring or a cycloalkyl ring, and at least one hydrogen in the formed ring is diarylamino or diarylboryl (even if the two aryls are bonded via a single bond or a linking group). may be replaced with
X ¹ , X ² and X ³ are each independently O, NR, provided that R in NR is alkyl, cycloalkyl, aryl or heteroaryl,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11') may be substituted with cyano, halogen, or deuterium. )

[20] A polycyclic aromatic compound represented by any of the following formulas.

The present invention provides a novel polycyclic aromatic compound useful as a material for organic devices such as organic electroluminescent elements. The present invention also provides materials that can be used to make this new compound. The polycyclic aromatic compound of the present invention can be used for manufacturing organic devices such as organic electroluminescent elements.

1 is a schematic cross-sectional view showing an example of an organic electroluminescent device.

In the following, the present invention will be explained in detail. Although the constituent elements described below may be explained based on typical embodiments and specific examples, the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after the "~" as lower and upper limits. Further, in this specification, "hydrogen" in the explanation of the structural formula means "hydrogen atom (H)".
In this specification, an organic electroluminescent device may be referred to as an organic EL device.

In this specification, chemical structures and substituents may be expressed by the number of carbon atoms, but when a chemical structure is substituted with a substituent, or when a substituent is further substituted with a substituent, the number of carbon atoms is It refers to the number of carbon atoms in each group, and does not mean the total number of carbon atoms in the chemical structure and substituents, or the total number of carbon atoms in the substituents. For example, "substituent B having a carbon number Y substituted with a substituent A having a carbon number X" means that "substituent B having a carbon number Y" is substituted with "substituent A having a carbon number X". However, the carbon number Y is not the total carbon number of substituent A and substituent B. For example, "substituent B having carbon number Y and substituted by substituent A" means that "substituent B having carbon number Y" is substituted with "substituent A (of which the number of carbon atoms is not limited)". However, the carbon number Y is not the total carbon number of substituent A and substituent B.

1. Polycyclic aromatic compounds and their multimers (complexes)
In Patent Documents 1 and 2, polycyclic aromatic compounds in which aromatic rings are connected with hetero elements such as boron, nitrogen, phosphorus, oxygen, and sulfur have a large HOMO-LUMO gap (band gap Eg in a thin film) and a high triplet. It has been found to have an excitation energy (E _T ). This is because the 6-membered ring containing the hetero element has low aromaticity, which suppresses the decrease in the HOMO-LUMO gap accompanying expansion of the conjugated system, and the electronic perturbation of the hetero element causes the triplet excited state (T1 ) is thought to be caused by the localization of SOMO1 and SOMO2. In addition, in the polycyclic aromatic compounds containing hetero elements described in Patent Documents 1 and 2, the exchange interaction between both orbitals is reduced due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). Since the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small and it exhibits thermally activated delayed fluorescence, it is also useful as a fluorescent material for organic EL devices. Further, a material having a high triplet excitation energy ( _ET ) is useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence. Furthermore, these polycyclic aromatic compounds can arbitrarily shift the HOMO and LUMO energies by introducing substituents, making it possible to optimize the ionization potential and electron affinity according to the surrounding materials. .

In the present invention, a polycyclic aromatic compound represented by the following formula (1), which is a complex having a structure similar to the polycyclic aromatic compound containing a hetero element described in Patent Documents 1 and 2, or a polycyclic aromatic compound represented by the following formula We have produced multimers of polycyclic aromatic compounds having multiple structures represented by (1) and found that they have similar properties.
The multimer of a polycyclic aromatic compound having a plurality of structures represented by formula (1) is preferably a polycyclic aromatic compound represented by the following formula (1') or a polycyclic aromatic compound represented by the following formula (1'). It is a multimer of polycyclic aromatic compounds having multiple structures.

Ring A, ring B, and ring C in formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. The substituents include substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and (amino group with heteroaryl), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted Preferred are diarylphosphine, substituted or unsubstituted diarylphosphine oxide, substituted or unsubstituted diarylphosphine sulfide, substituted or unsubstituted silyl, or substituted or unsubstituted diarylboryl. When these groups have a substituent, examples of the substituent include aryl, heteroaryl, and alkyl.

In addition, the above aryl ring or heteroaryl ring is a fused three-ring structure at the center of formula (1) comprising X ¹ , X ² , X ³ and Y (hereinafter, this structure is also referred to as "D structure") It is preferable to have a 5-membered ring or a 6-membered ring that shares a bond with.

Here, the term "fused three-ring structure (D structure)" refers to a structure in which three rings including X ¹ , X ² , X ³ and Y shown in the center of formula (1) are connected. means. Further, the term "6-membered ring sharing a bond with the connected 3-ring structure" means, for example, the a-ring (6-membered ring) fused to the D structure as shown in formula (1'). In addition, "the aryl ring or heteroaryl ring (which is Ring A) has this 6-membered ring" means that Ring A is formed only with this 6-membered ring, or that it contains this 6-membered ring. This means that the A ring is formed by condensing another ring with this 6-membered ring. In other words, the "aryl ring or heteroaryl ring having a 6-membered ring (which is the A ring)" as used herein means that the 6-membered ring constituting all or part of the A ring is fused to the D structure. It means there is. The same explanation applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

Z in formula (1) and formula (1') is a carbon atom or a nitrogen atom. Further, the "C ring (c ring)" always contains one nitrogen atom as represented by formula (1) and formula (1'). Therefore, the "C ring (c ring)" becomes a heteroaryl ring.

Ring A (or ring B or ring C) in formula (1) is ring a and its substituent R a (or ring b and its substituent R ^a , or ring c and its substituent ^{R a )} in formula (1'). ). That is, formula (1') corresponds to a formula in which "a ring A to C having a 6-membered ring" is selected as rings A to C in formula (1). In this sense, each ring in formula (1') is represented by lowercase letters a to c.

Z ^a each independently represents C-R ^a or N, or two adjacent Z ^a in the same ring together with the bond between them each represent N-R ^a , O, S or Se. show. For example, when Z ^a =Z ^a adjacent to ring c is NR ^a , ring c becomes a pyrrole ring.

In formula (1'), adjacent groups among the substituents R ^a of rings a, b, and c are bonded together to form an aryl ring or a heteroaryl ring with ring a, ring b, or ring c. and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, in which at least one The two hydrogens may be substituted with aryl, heteroaryl or alkyl. Therefore, the polycyclic aromatic compound represented by formula (1') has the following formula (1-1) and formula (1-2) depending on the mutual bonding form of the substituents in ring a, ring b, and ring c. As shown in , the ring structure constituting the compound changes. Ring A', ring B' and ring C' in each formula correspond to ring A, ring B and ring C in formula (1), respectively.

In formula (1-1) and formula (1-2), ring A', ring B', and ring C' are explained in terms of formula (1'), when adjacent groups of substituents R ^a Indicates an aryl ring, heteroaryl ring, or cycloalkyl ring formed by bonding with rings a, b, and c, respectively (a condensed ring formed by fusing another ring structure to ring a, b, or c) ). Although not shown in the formula, there are also compounds in which all of ring a, ring b, and ring c are changed to ring A', ring B', and ring C'. Furthermore, as can be seen from formula (1-1) and formula (1-2), for example, R ^a of ring a and R ^a of ring b, R ^a of ring b and R a of ring c, R ^a of ring c, ^A and R ^a of ring a, etc., do not fall under "adjacent groups" and do not bond together. That is, "adjacent groups" means groups that are adjacent on the same ring.

These compounds include, for example, a benzene ring, an indane ring (including dimethyl substituents, etc.), an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, a cyclopentane ring, or It is a compound having an A' ring (or B' ring or C' ring) formed by condensing cyclohexane rings, and the fused ring A' (or fused ring B' or fused ring C') formed by Each of them is a naphthalene ring, a fluorene ring (including a dimethyl substituted ring), a carbazole ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring, a dihydroindene ring, or a tetrahydronaphthalene ring.

In formula (1), X ¹ , X ² and X ³ are each independently O, NR, S or Se, and R in NR is optionally substituted aryl, unsubstituted optionally heteroaryl, alkyl or cycloalkyl, where at least one of X ¹ , X ² and X ³ is preferably NR, more preferably at least two are NR. Preferably, three are NR, more preferably. Furthermore, R in the NR may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond. The linking group is preferably -O-, -S-, -C(-R) ₂ -, >N-R, or arylene having 6 to 30 carbon atoms. Incidentally, R in the above "-C(-R) ₂ -" is hydrogen, alkyl or aryl. Further, R in the above ">NR" is alkyl or aryl which may be substituted with alkyl. This explanation is the same for X ¹ , X ² and X ³ in formula (1').

Here, in formula (1), the definition that "R in NR is bonded to the A ring, B ring and/or C ring through a linking group, single bond or condensation" is defined as the formula (1'). "R in NR is -O-, -S-, -C(-R) ₂ -, >NR, arylene having 6 to 12 carbon atoms, a single bond or condensation to form the a ring, b ring and / or bonded to the c-ring."

This regulation can be expressed by a compound having a ring structure represented by the following formula (1-3-a) in which X ² and X ¹ are incorporated into fused ring B' and fused ring C'. That is, for example, ^the B' ring ( ^or C' ring). The resulting fused ring B' (or fused ring C') is, for example, a phenoxazine ring, a phenothiazine ring, an acridine ring or a phenophosphazine ring.

In addition, the above provisions apply to compounds having a ring structure in which X ¹ and/ ^or But I can express it. That is, for example, it is a compound having an A' ring formed by condensing another ring such that X ¹ (and/or X ² ) is incorporated into the a ring in formula (1'). This compound corresponds to, for example, compounds represented by formulas (1-1-48) to formula (1-1-79) listed as specific compounds described later, and is formed by a condensed ring A. ' is, for example, a phenoxazine ring, a phenothiazine ring, an acridine ring or a phenophosphazine ring.

Although not specifically explained, the above provision includes a form in which R of NR of X ³ is bonded to ring B and/or ring C (ring b and/or ring c) through a linking group or a single bond. Also included. For example, a compound having a B' ring (or C' ring) formed by condensing the b ring (or c ring) in formula (1') with another ring so as to incorporate ^X3 . be.

Furthermore, the above definition also includes a composite form in which X ¹ , X ² or X ³ is incorporated into any of the condensed rings.

Examples of the "aryl ring" which is ring A and ring B in formula (1) include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, and an aryl ring having 6 to 12 carbon atoms. Aryl rings are more preferred, and aryl rings having 6 to 10 carbon atoms are particularly preferred. In addition, this "aryl ring" corresponds to "an aryl ring formed with ring a, ring b, or ring c by bonding adjacent groups of Z ^a " defined in formula (1'). Also, since ring a (or ring b, ring c) is already composed of a benzene ring with 6 carbon atoms, the lower limit of the number of carbon atoms in the fused ring with a 5-membered ring is 9. .

Specific "aryl rings" include a monocyclic benzene ring, a biphenyl ring, a fused bicyclic naphthalene ring, and a tricyclic terphenyl ring (m-terphenyl, o -terphenyl, p-terphenyl), fused tricyclic ring systems such as acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic ring system such as triphenylene ring, pyrene ring, naphthacene ring, benzofluorene ring, fused 5-ring system Examples include ring systems such as perylene ring and pentacene ring. Further, the fluorene ring and benzofluorene ring include a structure in which fluorene rings and benzofluorene rings are spiro-bonded.

Examples of the "heteroaryl ring" which is ring A, ring B, and ring C in formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, A heteroaryl ring having 2 to 20 carbon atoms is more preferred, a heteroaryl ring having 2 to 15 carbon atoms is even more preferred, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferred. Examples of the "heteroaryl ring" include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms. In addition, this "heteroaryl ring" is a "heteroaryl ring formed with ring a, ring b, or ring c by bonding adjacent groups of R ^a " defined in formula (1'). Correspondingly, since ring a (or ring b, ring c) is already composed of a benzene ring with 6 carbon atoms, the total number of carbon atoms in the condensed ring with a 5-membered ring is 6, which is the lower limit of the number of carbon atoms. becomes. However, the C ring is a heteroaryl ring always containing one nitrogen atom as represented by formula (1) or formula (1').

Specific "heteroaryl rings" include, for example, pyrrole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, imidazole rings (unsubstituted, substituted with alkyl such as methyl, or substituted with aryl such as phenyl), oxazole rings, Diazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring , benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxy ring Sadine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, naphthobenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, naphthobenzothiophene ring, benzophosphole ring , dibenzophosphole ring, benzophosphole oxide ring, dibenzophosphole oxide ring, furazane ring, oxadiazole ring, thianthrene ring, etc.

At least one hydrogen in the above "aryl ring" or "heteroaryl ring" is the first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl", substituted or unsubstituted "alkyl", substituted or Unsubstituted "cycloalkyl," substituted or unsubstituted "alkoxy," substituted or unsubstituted "aryloxy," substituted or unsubstituted "arylsulfonyl," substituted or unsubstituted "diarylphosphine," substituted or unsubstituted It may be substituted with a substituted "diarylphosphine oxide" or a substituted or unsubstituted "diarylphosphine sulfide", but "aryl", "heteroaryl", "diarylamino" as the first substituent aryl of "diheteroarylamino", aryl and heteroaryl of "arylheteroarylamino", aryl of "diarylboryl", aryl of "aryloxy", aryl of "arylsulfonyl", "diarylphosphine" Examples of the aryl, the aryl in "diarylphosphine oxide", the aryl in "diarylphosphine sulfide", and the aryl in "diarylborane" include monovalent groups of the above-mentioned "aryl ring" or "heteroaryl ring".

Specific examples of "aryl" include phenyl, which is a monocyclic system, biphenylyl, which is a bicyclic system, naphthyl (1-naphthyl or 2-naphthyl), which is a fused bicyclic system, and terphenylyl (m-terphenylyl, which is a tricyclic system). , o-terphenylyl or p-terphenylyl), fused tricyclic ring systems such as acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, fused tetracyclic ring systems such as triphenylenyl, pyrenyl, naphthacenyl, and fused pentacyclic ring systems such as perylenyl and pentacenyl. .

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

Specific examples of "heteroaryl" include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H- indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxatiinyl, phenoxazinyl, phenothiazinyl, Examples include phenazinyl, indolizinyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thiophenyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, furazanyl, and thianthrenyl.

Further, the "alkyl" as the first substituent may be either straight chain or branched chain, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms is preferable. (branched alkyl having 3 to 6 carbon atoms) is more preferred, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

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

Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1,1,2- Trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3- Dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1 -Propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl and the like can also be mentioned.

Examples of "cycloalkyl" as the first substituent include cycloalkyl having 3 to 12 carbon atoms. Preferred cycloalkyl is a cycloalkyl having 3 to 10 carbon atoms. More preferred cycloalkyl is cycloalkyl having 3 to 8 carbon atoms. More preferred cycloalkyl is cycloalkyl having 3 to 6 carbon atoms.

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituted products having 1 to 5 carbon atoms, norbornenyl, bicyclo[1 .0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2 .1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl, and the like.

Note that by introducing cycloalkyl into the compound of the present invention, a reduction in the melting point and sublimation temperature can be expected. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL elements that require high purity, thermal decomposition of the material can be avoided because purification can be performed at a relatively low temperature. means. This also applies to the vacuum evaporation process, which is an effective means for producing organic devices such as organic EL elements, and because the process can be carried out at relatively low temperatures, thermal decomposition of the material can be avoided. As a result, a high-performance organic device can be obtained. Furthermore, since the solubility in organic solvents is improved by the introduction of cycloalkyl, it can also be applied to device fabrication using a coating process. However, the present invention is not particularly limited to these principles.

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

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

"diarylamino" (first substituent), "diheteroarylamino" (first substituent), "arylheteroarylamino" (first substituent), "aryloxy" (first substituent), "aryl "aryl" and "sulfonyl" (first substituent), "diarylphosphine" (first substituent), "diarylphosphine oxide" (first substituent), and "diarylphosphine sulfide" (first substituent) For details of "heteroaryl", the above explanation of "aryl" and "heteroaryl" can be cited.

Examples of the "substituted silyl" as the first substituent include trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, which is silyl substituted with alkyl and/or cycloalkyl. can be given.

"Trialkylsilyl" includes a group in which three hydrogens in a silyl group are each independently substituted with alkyl, and this alkyl refers to the group explained as "alkyl" in the first substituent group above. be able to. Preferred alkyls for substitution are those having 1 to 5 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, and t-amyl.

Specific trialkylsilyl includes trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-t-butylsilyl, tri-t-amylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, t-amyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethyl Silyl, t-butyldiethylsilyl, t-amyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, t-amyldipropylsilyl, Examples include methyldi-i-propylsilyl, ethyldi-i-propylsilyl, butyldi-i-propylsilyl, sec-butyldi-i-propylsilyl, t-butyldi-i-propylsilyl, t-amyldi-i-propylsilyl, and the like.

"Tricycloalkylsilyl" includes a group in which each of the three hydrogen atoms in a silyl group is independently substituted with cycloalkyl, and this cycloalkyl is the same as the "cycloalkyl" in the first substituent described above. The group can be cited. Preferred cycloalkyl for substitution is cycloalkyl having 5 to 10 carbon atoms, specifically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.0.1] pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, Examples include decahydronaphthalenyl and decahydroazulenyl.

Specific examples of tricycloalkylsilyl include tricyclopentylsilyl and tricyclohexylsilyl.

Specific examples of dialkylcycloalkylsilyl substituted with two alkyl and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyl are selected from the above-mentioned specific alkyl and cycloalkyl. Examples include silyl substituted with a group.

Further, as for "aryl" in "diarylboryl" as the first substituent, the above explanation of aryl can be cited. Further, these two aryls may be bonded via a single bond or a linking group (eg, >C(-R) ₂ , >O, >S or >NR). Here, R in >C(-R) ₂ and >N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (the above is a first substituent), and the first 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 the aryl, heteroaryl, and heteroaryl as the first substituent described above. References may be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.

The emission wavelength can be adjusted depending on the steric hindrance, electron donating and electron withdrawing properties of the structure of the first substituent. Preferably it is a group represented by the following structural formula, more preferably methyl, t-butyl, t-amyl, t-octyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2, 5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl , 3,6-di-t-butylcarbazolyl 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, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl It is le. From the viewpoint of ease of synthesis, those with greater steric hindrance are preferable for selective synthesis. Specifically, t-butyl, t-amyl, t-octyl, o-tolyl, p-tolyl, 2 ,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, 3,6-dimethylcarba Zolyl and 3,6-di-t-butylcarbazolyl are preferred.

In the structural formula below, "Me" represents methyl, "tBu" represents t-butyl, "tAm" represents t-amyl, and "tOct" represents t-octyl.

In formula (1'), 0 to 4 of R ^a are groups represented by any of the above structural formulas, and the remainder is preferably hydrogen, and 0 to 3 of R ^a is a group represented by any of the above structural formulas, and the remainder is preferably hydrogen.

The first substituent is substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", substituted or unsubstituted "aryloxy", substituted or unsubstituted "arylsulfonyl", substituted or unsubstituted "diarylphosphine", substituted or unsubstituted "diarylphosphine oxide", substituted or unsubstituted "diarylphosphine sulfide" are described as substituted or unsubstituted, and at least one hydrogen therein may be substituted with a second substituent. Examples of the second substituent include aryl, heteroaryl, or alkyl, and specific examples thereof include the monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring," and the first substituent. Reference may be made to the explanation of "alkyl" as a group. Furthermore, in aryl and heteroaryl as the second substituent, at least one hydrogen thereof is substituted with an aryl such as phenyl (specific examples are the groups mentioned above) or an alkyl such as methyl (specific examples are the groups mentioned above). It also includes groups. For example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl or an alkyl such as methyl can also be used as a heterosubstituent. Included in aryl.

As the aryl, heteroaryl, aryl of diarylamino, heteroaryl of diheteroarylamino, aryl and heteroaryl of arylheteroarylamino, aryl of diarylboryl, or aryl of aryloxy in R ^a of formula (1'), Examples include the monovalent group of the "aryl ring" or "heteroaryl ring" explained in formula (1), and any substituent is the same substituent as the first substituent in the explanation of formula (1) above. You can refer to the explanation. Further, for the alkyl or alkoxy in R ^a , the explanation of "alkyl" or "alkoxy" as the first substituent in the explanation of formula (1) above can be referred to. Furthermore, the same applies to aryl, heteroaryl or alkyl as a substituent to these groups. In addition, when adjacent groups of R ^a combine to form an aryl ring or a heteroaryl ring with the a-ring, b-ring or c-ring, the heteroaryl or diarylamino substituent to these rings , diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, and the further substituents aryl, heteroaryl or alkyl.

In formula ( ¹ ), R in NR in X ¹ , X ² and At least one hydrogen in may be substituted with, for example, alkyl. Specific examples of this aryl, heteroaryl, alkyl or cycloalkyl include the groups mentioned above. Particularly preferred are aryl having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (eg, carbazolyl, etc.), and alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.). This explanation is the same for X ¹ , X ² and X ³ in formula (1').

R in "-C(-R) ₂ -" which is a linking group in formula (1) is hydrogen, alkyl or aryl, and R in ">N-R" is alkyl or aryl optionally substituted with alkyl. However, specific examples of this alkyl and aryl include the groups mentioned above. Particularly substituted with alkyl having 1 to 6 carbon atoms, alkyl having 1 to 4 carbon atoms (e.g. methyl, ethyl, etc.), alkyl having 1 to 6 carbon atoms, alkyl having 1 to 4 carbon atoms (e.g. methyl, ethyl, etc.) Aryl having 6 to 12 carbon atoms (phenyl, naphthyl, etc.) is preferred. This explanation is the same for "-C(-R) ₂ --" and ">NR" which are linking groups in formula (1').

Furthermore, the linking group "arylene" and "arylene having 6 to 30 carbon atoms" in formula (1) include divalent groups having the same structure as the above-mentioned aryl. This explanation is the same for "arylene having 6 to 12 carbon atoms" which is a linking group in formula (1').

Y in formula (1) and formula (1') is a metal of Groups 3 to 11 of the periodic table that is coordinated with a ligand, or a metal of Groups 13 to 14 of the periodic table that is coordinated with a ligand. Indicates a metal or metalloid, or a metalloid of groups 15-16 of the periodic table that is coordinated with a ligand. The semimetals of Groups 13 and 14 of the periodic table include boron (B), silicon (Si), and germanium (Ge). Arsenic (As) and tellurium (Te) are examples of metalloids belonging to Groups 15 and 16 of the periodic table. The metal or semimetal in Y is preferably B (boron) or Ir (iridium), and more preferably B (boron).

In the structures represented by formula (1) and formula (1'), it is shown that the above metal or metalloid in Y is already coordinated to the tridentate ligand, and In addition to the above-mentioned tridentate ligand, the ligand is a ligand that coordinates to the above-mentioned metal or metalloid. Usually, the coordination number of the metal or metalloid in the structure represented by formula (1) is 4 to 6 depending on the type. Therefore, the coordination number of the ligand in Y is usually 1 to 3, depending on the above-mentioned metal or metalloid in Y. For example, in the case of B (boron), there are four coordinations, and the number of coordinations of the ligand in Y is one. Further, in the case of Ir (iridium), it is 4-or 6-orientated, and the number of ligands in Y is 1 or 3, respectively.
When there is a plurality of ligands in Y, the plurality of ligands may be the same or different.

The ligand in Y may be a monodentate ligand or a polydentate ligand such as a bidentate ligand, but a monodentate ligand is preferable. Examples of ligands for Y include aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl, sulfonate, pyridine, cyanide ion, halogen ion, hydroxide ion, oxo ion, Examples include trialkylphosphine, triarylphosphine, cyclooctadiene, carbon monoxide, and water. The ligand for Y is preferably aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl or sulfonate. The ligand may be only the above preferred examples, but in addition to any of the above preferred examples, pyridine, cyanide ion, halogen ion, hydroxide ion, oxo ion, trialkylphosphine, triaryl Phosphine, cyclooctadiene, carbon monoxide, water, or the like may be coordinated.
The ligand in Y may be, for example, an axial ligand that coordinates in the axial direction with respect to the plane formed by the polycyclic aromatic ring in formula (1).

The ligand in Y is preferably selected depending on the metal or metalloid used so that the structure represented by formula (1) and formula (1') as a whole is electrically neutral. . When the structure represented by formula (1) and formula (1') as a whole is not electrically neutral, it may be combined with an inorganic ion such as a sodium ion or a potassium ion to form a salt.

Preferably, Y is a metal or metalloid coordinated with one monodentate ligand.
More preferably, Y is represented by MR ^x . M is B (boron) or Ir (iridium). R ^x is aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl and sulfonate.

Specific examples of aryl, alkyl, alkoxy and aryloxy as R ^x include the groups mentioned above. In particular, aryl having 6 to 12 carbon atoms, aryl having 6 to 10 carbon atoms (e.g. phenyl, naphthyl, etc.), alkyl having 1 to 6 carbon atoms, alkyl having 1 to 4 carbon atoms (e.g. methyl, ethyl, etc.), Preferred are alkoxy having 6 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms (eg, methoxy, ethoxy, etc.), aryloxy having 6 to 12 carbon atoms, and aryl having 6 to 10 carbon atoms (eg, phenyloxy, naphthyloxy, etc.). Furthermore, examples of halogen include F, Cl, Br and I.

The above "cyclopentadienyl" includes not only cyclopentadienyl but also those substituted with alkyl such as pentamethylcyclopentadienyl. Cp) or pentamethylcyclopentadienyl (Cp*) are preferred.

The above-mentioned "sulfonate" includes sulfonates substituted with aryl or alkyl, as well as sulfonates substituted with fluorine-substituted alkyl such as trifluoromethyl.

Specific examples of sulfonates include methanesulfonate (mesylate), p-toluenesulfonate (tosylate), trifluoromethanesulfonate (triflate), and nonafluorobutanesulfonate (nonaflate).

In addition, when R ^x of the above M-R ^x is a sulfonate, more precisely, it exists as an ion pair as shown on the left side of the formula below, and R ^x of the above M-R ^x is a cyclopentadienyl ( Here, in the case of pentamethylcyclopentadienyl (Cp* will be explained as an example), it has a semi-sandwich shape as shown on the left side of the formula below, but in this specification, for convenience, M-R ^x It is written in the format.

The compound of the present invention includes a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by formula (1), preferably a polycyclic aromatic compound having a plurality of unit structures represented by formula (1'). Also included are multimers of the compounds. Preferably, the multimer is a dimer. The dimer may have two of the above unit structures in one compound. For example, the above unit structure may be a single bond, a linkage of an alkylene group having 1 to 3 carbon atoms, a phenylene group, a naphthylene group, etc. In addition to the form in which two groups are bonded, any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above unit structure is shared by two unit structures. It may be in a bonded form, or in a bonded form in which any rings (A ring, B ring or C ring, a ring, b ring or c ring) included in the above unit structure are condensed with each other. There may be.

Examples of such dimers include dimers represented by the following formula (1-4), formula (1-5), or formula (1-6). That is, if explained using formula (1'), it is a dimer having two unit structures represented by formula (1') in one compound so that the benzene ring which is the a ring is shared. . In addition, if the dimer represented by the following formula (2-5) is explained using the formula (1'), the dimer of the two formulas (1') shares ^X2 with the benzene ring which is the a ring. ) is a dimer having a unit structure represented by the following in one compound. That is, in the formula (1'), for example, a benzene ring is the a-ring (or b-ring, c-ring) of a certain unit structure, and a benzene ring is the a-ring (or b-ring, c-ring) of a certain unit structure. It is a dimer having two unit structures represented by formula (1') in one compound such that the two are condensed.

Examples of such dimers include dimers represented by the following formula (1-4), formula (1-5), or formula (1-6). Note that the definitions of Y, X ¹ , X ² , X ³ , Z ^a and Z in the following formula are the same as those in formula (1').

Furthermore, even if all or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by formula (1) or formula (1') and its dimer is cyano, halogen, or deuterium, good. For example, in formula (1), when the A ring, the B ring, the C ring (A to C rings are aryl rings or heteroaryl rings), the substituents to A to C rings, and Y is MR ^x , R ^x (=aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl and sulfonate) and R (=alkyl when X ¹ , X ² and X ³ are NR) , aryl) may be substituted with cyano, halogen, or deuterium, and examples include embodiments in which all or part of cyano or hydrogen in aryl or heteroaryl is substituted with halogen or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine.

Specific examples of the polycyclic aromatic compound represented by formula (1) include compounds represented by the following structural formula. In the structural formula below, Me is methyl, tBu is tert-butyl, D is deuterium, Ph is phenyl, TfO is trifluoromethanesulfonate (CF ₃ S(O) ₂ O-), and Cp is cyclopentane. Dienyl, Cp* is pentamethylcyclopentadienyl.

2. Polycyclic aromatic compounds and their multimers (ligands)
The above complex is produced using a polycyclic aromatic compound represented by the following formula (11) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11), as described below. be able to. The polycyclic aromatic compound represented by the following formula (11) or the multimer of the polycyclic aromatic compound having a plurality of structures represented by the following formula (11) is preferably represented by the following formula (11'). or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11'). These polycyclic aromatic compounds can function as ligands in complexes. In particular, it can function as a tridentate ligand in the polycyclic aromatic compound represented by the above formula (1) or formula (1') and its multimer.
The polycyclic aromatic compound represented by formula (11) or formula (11') and its polymer are metal-containing complexes or metalloid-containing complexes, especially those represented by formula (1) or formula (1') above. It can be used to synthesize polycyclic aromatic compounds or complexes that are multimers thereof.

The definitions of ring A, ring B, and ring C in formula (11) are the same as those in formula (1) and formula (1'), but ring B differs in that Z is ^Z The rings differ in the bond site to Y in formula (1). The C ring is preferably a ring having a structure in which the bond to Y in formula (1) is bonded to hydrogen.

In addition, the above aryl ring or heteroaryl ring shares a bond with the central ring structure of formula (11) containing X ¹ , X ² and X ³ (hereinafter, this structure is also referred to as "E structure"). It is preferable to have a 5-membered ring or a 6-membered ring.

In formula (11) and formula (11'), Z ^x represents CH or N. When Z ^a is CH in formula (11) and formula (11'), Z is a carbon atom in the compounds of formula (1) and formula (1') produced using it.

Here, the "6-membered ring sharing a bond with the E structure" means, for example, a ring fused to the E structure as shown in formula (11'). In addition, "the aryl ring or heteroaryl ring (which is Ring A) has this 6-membered ring" means that Ring A is formed only with this 6-membered ring, or that it contains this 6-membered ring. This means that the A ring is formed by condensing another ring with this 6-membered ring. In other words, the term "aryl ring or heteroaryl ring having a 6-membered ring (which is the A ring)" as used herein means that the 6-membered ring constituting all or part of the A ring is the E
It means that it is condensed into a structure. The same explanation applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

Ring A (or ring B, ring C) in formula (11) is ring a and its substituent R ^a (or ring b and its substituent R a , ^or ring c and its substituent R a ) in formula (11') ^. ). That is, formula (11') corresponds to a formula in which "ring A to C having a 6-membered ring" is selected as rings A to C in formula (11). In this sense, each ring in formula (11') is represented by lowercase letters a to c.

In formula (11'), adjacent groups among the substituents R ^a of ring a, ring b, and ring c combine to form an aryl ring or a heteroaryl ring with ring a, ring b, or ring c. and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, in which at least one The two hydrogens may be substituted with aryl, heteroaryl or alkyl. Therefore, the polycyclic aromatic compounds represented by the formula (1) and the formula (1') have the following formula (11-1) and the formula As shown in (11-2), the ring structure constituting the compound changes. Ring A', ring B' and ring C' in each formula correspond to ring A, ring B and ring C in formula (11), respectively.

In formulas (11-1) and (11-2), A' ring, B' ring, and C' ring are bonded to each other when adjacent groups of substituents R ^a are bonded to each other. represents an aryl ring or a heteroaryl ring formed with ring a, ring b, and ring c, respectively (it can also be said to be a fused ring formed by condensing another ring structure with ring a, ring b, or ring c). Although not shown in the formula, there are also compounds in which all of ring a, ring b, and ring c are changed to ring A', ring B', and ring C'. Furthermore, as can be seen from formula (11-1) and formula (11-2), for example, R a of ring ^a and R ^a of ring b, R a of ring b and ^{R a} of ring c, R ^a of ring c ^A and R ^a of ring a, etc., do not fall under "adjacent groups" and do not bond together. That is, "adjacent groups" means groups that are adjacent on the same ring.

The compound represented by formula (11-1) or formula (11-2) is, for example, (11-1-88), (11-1-89) or (11-1- 90). These compounds include, for example, a benzene ring, an indane ring (including dimethyl substituents, etc.), an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, a cyclopentane ring, or It is a compound having an A' ring (or B' ring or C' ring) formed by condensing cyclohexane rings, and the fused ring A' (or fused ring B' or fused ring C') formed by Each of them is a naphthalene ring, a fluorene ring (including a dimethyl substituted ring), a carbazole ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring, a dihydroindene ring, or a tetrahydronaphthalene ring.

X ¹ , X ² and X ³ in formula (11) and formula (11') have the same meanings as defined in formula (1) and formula (1').

The above definition also applies to a compound represented by the following formula (11-3-a) having a ring structure in which X ² or X ¹ is incorporated into the fused ring B' and the fused ring C'.
In addition, the above definition applies to compounds having a ring structure in which X ¹ and/ ^or But it is applied

Although not specifically explained, the above definition includes a form in which R in NR of X ³ is bonded to ring B and/or ring C (ring b and/or ring c) through a linking group or a single bond. is also included, and the explanation above applies to its explanation. For example, it corresponds to compounds represented by formulas (11-1-48) to (11-1-87) listed as specific compounds described later.

Furthermore, the above definition also includes a composite form in which X ¹ , X ² or X ³ is incorporated into any of the condensed rings, and the above description applies to the explanation thereof.

In formula (11) and formula (11') ^{, R in NR in X 1 ,} X ² and Yes, and the explanations in equations (1) and (1') above apply.

In formula (11) and formula (11'), R in "-C(-R) _2- " which is a linking group is hydrogen, alkyl or aryl, and R in ">N-R" is substituted with alkyl or alkyl. is an aryl which may be expressed as an aryl, and the explanations in the above formulas (1) and (1') apply.

Furthermore, the linking group "arylene" and "arylene having 6 to 30 carbon atoms" in formulas (11) and (11') include divalent groups having the same structure as the above-mentioned aryl.

In addition, the compound of the present invention as a ligand includes a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by formula (11) or formula (11'), preferably a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by formula (11) or (11'). Also included are multimers of polycyclic aromatic compounds having a plurality of unit structures represented by the following. Preferably, the multimer is a dimer. The dimer may have two of the above unit structures in one compound. For example, the above unit structure may be a single bond, a linkage of an alkylene group having 1 to 3 carbon atoms, a phenylene group, a naphthylene group, etc. In addition to the form in which two groups are bonded, any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above unit structure is shared by two unit structures. It may be in a bonded form, or in a bonded form in which any rings (A ring, B ring or C ring, a ring, b ring or c ring) included in the above unit structure are condensed with each other. There may be.

Examples of such dimers include dimers represented by the following formula (11-4), formula (11-5), or formula (11-6). Note that the definitions of X ¹ , X ² , X ³ , Z ^a and Z in the following formula are the same as those in formula (11').

Further, all or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by formula (11) or (11') and its polymer may be cyano, halogen, or deuterium. For example, in formula (11), ring A, ring B, ring C (rings A to C are aryl rings or heteroaryl rings), substituents to rings A to C, and X ¹ , X ² and X ³ When is NR, hydrogen in R (=alkyl, aryl) may be substituted with cyano, halogen, or deuterium, but among these, all or part of cyano or hydrogen in aryl or heteroaryl may be substituted with halogen or deuterium. Examples include hydrogen-substituted embodiments. Halogen is fluorine, chlorine, bromine or iodine.

Specific examples of the polycyclic aromatic compound represented by formula (11) include compounds represented by the following structural formula. In the following structural formula, Me is methyl and tBu is tert-butyl.

3. Process for producing polycyclic aromatic compounds and multimers thereof Basically, the polycyclic aromatic compounds represented by formulas (1) and (1') and multimers thereof are produced by first forming a ring A (ring a) and a multimer thereof. Formula (11), which becomes an intermediate by bonding ring B (ring b) and ring C (ring c) with a bonding group (group containing X ¹ , X ² , and X ³ ), and formula (11'), The expressed polycyclic aromatic compound and its polymer are produced (first reaction), and then A ring (a ring), B ring (b ring) and C ring (c ring) are attached to a bonding group (Y (2nd reaction). That is, the polycyclic aromatic compounds represented by formula (11) and formula (11') and their polymers are the polycyclic aromatic compounds represented by formula (1) and formula (1') and their polymers. Used as raw material for manufacturing.

For the first reaction, for example, a general reaction such as a nucleophilic substitution reaction or an Ullmann reaction can be used for an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used for an amination reaction. Further, in the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. In addition, in the following scheme, the definitions of Y, X ¹ , X ² , X ³ , Z ^a , Z ^a and Z are the same as those in formula (1) or formula (1′).

The second reaction is a reaction in which Y is introduced to bond ring A (ring a), ring B (ring b), and ring C (ring c), as shown in schemes (1) and (2) below, As an example, the case where Y is B-Br and X ¹ , X ² and X ³ are nitrogen atoms will be shown below. The desired product can be obtained by adding boron trichloride and causing a tandem bola-Friedel-Crafts reaction. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

Note that the above schemes (1) and (2) mainly show methods for producing polycyclic aromatic compounds represented by formulas (1) and (1'); It can be produced by using an intermediate having an A ring (a ring), a B ring (b ring) and a C ring (c ring). Details will be explained in the following schemes (3) to (4). In this case, the desired product can be obtained by doubling the amount of the reagent such as boron trichloride used.

In the above synthesis method, the case where M in M-R ^x which is Y is a boron atom and R ^x is a bromine atom has been explained, but the bromine atom which is R ^x can be replaced with another one. That is, by using a phenyl Grignard reagent as shown in Scheme (7) below, R ^x is phenyl, and by using silver trifluoromethanesulfonate as shown in Scheme (8) below, R ^x is triflate. Each item can be manufactured.

Next, as an example, cases where Y is Ir-Cp* and X ¹ , X ² and X ³ are nitrogen atoms are shown in the following schemes (9) and (10). Treat with n-butyllithium, etc. Next, the desired product can be obtained by adding dichloro(pentamethylcyclopentadienyl)iridium(III) dimer ([Cp*IrCl ₂ ] _2. Here, sodium acetate etc. are added to accelerate the reaction. Good too.

In addition, when Y is Ir-Cp* and X ¹ , X ^{2 and} (12)).

In addition, in formula (11'), adjacent groups among the substituents R ^a of rings a, b, and c are bonded to each other, and together with rings a, b, or c, an aryl ring, a heteroaryl ring, or a cyclo It may form an alkyl ring, and at least one hydrogen in the ring formed may be substituted with alkyl, cycloalkyl, aryl or heteroaryl. Therefore, the coordination compound of the polycyclic aromatic compound represented by formula (11') can be expressed in the following schemes (13) and (14) depending on the mutual bonding form of the substituents in the a-ring, b-ring, and c-ring. As shown, the ring structure constituting the compound changes. These compounds can be synthesized by applying the synthesis methods shown in the above schemes (1) to (12) to the intermediates shown in the following schemes (13) and (14).

In the above formula, A' ring, B' ring, and C' ring are aryl rings and heteroaryl rings formed by bonding adjacent groups of substituent R ^a together with a ring, b ring, and c ring, respectively. ring or cycloalkyl ring (it can also be said to be a fused ring formed by condensing another ring structure with ring a, ring b, or ring c). Although not shown in the formula, there are also compounds in which all of ring a, ring b, and ring c are changed to ring A', ring B', and ring C'.

In addition, in formula (11'), "R of NR is -O-, -S-, -C(-R) ₂ -, >NR, arylene, a single bond or fused ring and/or bonded to ring c" means that X ¹ and X ² are bonded to fused ring B' and fused ring C', which is Compounds with a ring structure incorporated into the fused ring A', or compounds with a ring structure in which X ^{1 or} It can be expressed as a compound that has These compounds can be synthesized by applying the synthesis methods shown in schemes (1) to (14) above to the intermediate shown in scheme (15) below.

The Lewis acids used in the above schemes (1) to (4) and (7) to (15) 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, Cu(OTf) ₂ , CuCl ₂ , YCl ₃ , Y(OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr ₃ and the like.

In the above schemes (1) to (4) and (7) to (15), a Brønsted base or a Lewis acid may be used to promote the tandem hetero Friedel-Crafts reaction. However, when using a halide of Y 1 such as Y ¹ trifluoride, Y ¹ trichloride, Y ¹ tribromide, ^{Y 1} triiodide, etc., as the aromatic electrophilic substitution reaction progresses. Since acids such as , hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced, it is effective to use a Brønsted base to scavenge the acids. On the other hand, when an aminated halide of Y ¹ or an alkoxylated compound of Y ¹ is used, a Brønsted base is often used because amines and alcohols are generated as the aromatic electrophilic substitution reaction progresses. Although not necessary, since the ability to eliminate amino groups and alkoxy groups is low, it is effective to use a Lewis acid that promotes their elimination.

In addition, the polycyclic aromatic compounds and their dimers of the present invention include compounds in which at least some of the hydrogen atoms are substituted with cyano, compounds in which deuterium is substituted, and fluorine, chlorine, etc. This includes compounds substituted with halogens, but such compounds can be synthesized in the same manner as above by using raw materials that are cyanated, deuterated, fluorinated, or chlorinated at the desired site. be able to.

4. Organic Device The compound of the present invention (the above-mentioned polycyclic aromatic compound and its multimer), especially the compound of the present invention which is a complex, can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, and an organic thin film solar cell.

4-1. Organic electroluminescent device <Structure of organic electroluminescent device>
FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element.
The organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a A hole transport layer 104 provided, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and a light emitting layer 105 provided on the electron transport layer 106. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

Note that the organic EL element 100 can be manufactured in the reverse order, for example, by forming a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, and an electron injection layer 107. an electron transport layer 106 provided on the electron transport layer 106; a light emitting layer 105 provided on the electron transport layer 106; a hole transport layer 104 provided on the light emitting layer 105; It is also possible to have a configuration including a hole injection layer 103 provided on the hole injection layer 103 and an anode 102 provided on the hole injection layer 103.

All of the above layers are not indispensable, and the minimum structural unit is the anode 102, the light emitting layer 105, and the cathode 108. Layer 107 is an optional layer. Moreover, each of the above layers may be composed of a single layer or a plurality of layers.

In addition to the above-mentioned configuration of "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", examples of the layers constituting the organic EL element include " "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/ Anode / 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 / Anode/Emissive layer/Electron transport layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive 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" /light emitting layer/electron transport layer/cathode" or "substrate/anode/light emitting layer/electron injection layer/cathode" may be used.

<Light-emitting layer in organic electroluminescent device>
The compound of the present invention is preferably used as a material for forming one or more organic layers in an organic electroluminescent device, and more preferably used as a material for forming a light emitting layer.
The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between the electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be any compound (luminescent compound) that emits light when excited by recombination of holes and electrons, can form a stable thin film shape, and is in a solid state. It is preferable that the compound is a compound that exhibits strong luminescence (fluorescence) efficiency.
The compound of the present invention can be used as a material for a light-emitting layer, and may be used as a dopant material or together with a host material.

The light-emitting layer may be a single layer or composed of multiple layers, and each is formed from a material for the light-emitting layer (host material, dopant material). The host material and the dopant material may each be one type or a combination of a plurality of types. The dopant material may be contained entirely or partially in the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may also be mixed with the host material in advance and then vapor-deposited at the same time.

The amount of host material used varies depending on the type of host material, and may be determined depending on the characteristics of the host material. The amount of host material to be used is preferably 50 to 99.999% by mass, more preferably 80 to 99.95% by mass, and even more preferably 90 to 99.9% by mass of the entire material for the light emitting layer. It is.

The amount of dopant material to be used varies depending on the type of dopant material, and may be determined according to the characteristics of the dopant material. The amount of the dopant to be used is preferably 0.001 to 50% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.1 to 10% by mass based on the entire material for the light emitting layer. be. The above range is preferable in that, for example, concentration quenching phenomenon can be prevented.

Examples of host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene, or fluorene, which have long been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. , fluorene derivatives, benzofluorene derivatives, dibenzochrysene compounds, and the like.

Further, as the host material, for example, a compound represented by any one of the following formulas (H1), (H2), and (H3) can be used.

In formulas (H1), (H2) and (H3), L ¹ represents arylene having 6 to 24 carbon atoms, heteroarylene having 2 to 24 carbon atoms, heteroarylene arylene having 6 to 24 carbon atoms, and arylene having 6 to 24 carbon atoms. Arylene Heteroarylene Arylene, preferably arylene having 6 to 16 carbon atoms, more preferably arylene having 6 to 12 carbon atoms, particularly preferably arylene having 6 to 10 carbon atoms, specifically, benzene ring, biphenyl ring, Divalent groups such as terphenyl rings and fluorene rings may be mentioned. The heteroarylene is preferably a heteroarylene having 2 to 24 carbon atoms, more preferably a heteroarylene having 2 to 20 carbon atoms, even more preferably a heteroarylene having 2 to 15 carbon atoms, and particularly a heteroarylene having 2 to 10 carbon atoms. Preferably, specifically, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole 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, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring , quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring , dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, and thianthrene ring.
At least one hydrogen in the compounds represented by the above formulas may be substituted with alkyl having 1 to 6 carbon atoms, cyano, halogen, or deuterium.

Preferred specific examples include compounds 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 (eg, methyl or t-butyl), phenyl, or naphthyl.

Moreover, the dopant material is not particularly limited, and known compounds can be used, and can be selected from various materials depending on the desired emission color. Specifically, for example, fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives (JP-A-1-245087), bisstyrylarylene derivatives (JP-A-2-247278), diazaindacene derivatives, furan derivatives, benzofuran derivatives, 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- Coumarin derivatives such as methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, Examples include 1,2,5-thiadiazolopyrene derivatives, pyrromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives.
It is also preferable to use polycyclic aromatic compounds described in International Publication No. 2015/102118 and the like.

Examples of blue to blue-green dopant materials for each colored light include aromatic hydrocarbon compounds and their derivatives such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, and chrysene, furan, pyrrole, thiophene, Aromatic complexes such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene, etc. Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and their metal complexes and N , N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine.

Examples of green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene. - Suitable examples include compounds in which substituents such as aryl, heteroaryl, arylvinyl, amino, and cyano that enable longer wavelengths are introduced into the compounds exemplified as blue-green dopant materials.

Further, as orange to red dopant materials, naphthalimide derivatives such as bis(diisopropylphenyl)perylenetetracarboxylic acid imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, etc. -(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, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazone derivatives and thiadiazolopyrene derivatives, and further exemplified as the blue to blue-green and green to yellow dopant materials. Suitable examples include compounds in which a substituent such as aryl, heteroaryl, arylvinyl, amino, or cyano that enables a longer wavelength is introduced into the compound.

In addition, the dopant can be appropriately selected from among the compounds described in Kagaku Kogyo, June 2004 issue, page 13, and the references cited therein.

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic EL element 100, and is usually made of quartz, glass, metal, plastic, or the like. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape depending on the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among these, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferred. If it is a glass substrate, soda lime glass or non-alkali glass may be used, and the thickness may be sufficient to maintain mechanical strength, for example, 0.2 mm or more. 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, alkali-free glass is preferable because fewer ions elute from the glass, but soda lime glass coated with a barrier coating such as SiO ₂ is also commercially available, so it is recommended to use this. can. In addition, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side of the substrate 101 in order to improve gas barrier properties. In particular, a synthetic resin plate, film, or sheet with low gas barrier properties may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 plays the role of injecting holes into the light emitting layer 105. Note that when the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these. .

Examples of materials forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide, etc.). (IZO, etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, etc. Examples of the organic compound include polythiophenes such as poly(3-methylthiophene), conductive polymers such as polypyrrole, and polyaniline. In addition, materials that are used as anodes for organic EL devices may be selected as appropriate.

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

<Hole injection layer and hole transport layer in 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. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one or more hole injection/transport materials, or by a mixture of a hole injection/transport material and a polymer binder. be done. Alternatively, the layer may be formed by adding an inorganic salt such as iron(III) chloride to the hole injection/transport material.

As a hole injection/transport material, it is necessary to efficiently inject and transport holes from the positive electrode between the electrodes where an electric field is applied, and the material has high hole injection efficiency and efficiently transports the injected holes. It is desirable to do so. For this purpose, it is preferable to use a substance that has a low ionization potential, high hole mobility, excellent stability, and does not easily generate trapping impurities during production and use.

Materials for forming the hole injection layer 103 and the hole transport layer 104 include compounds conventionally used as hole charge transport materials in photoconductive materials, p-type semiconductors, and hole injection layers of organic EL devices. Any compound can be selected and used from among the known compounds used in the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine derivatives (4,4', 4"-tris(N-carbazolyl)triphenylamine, polymer with aromatic tertiary amino in main chain or side chain, 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 , triphenylamine derivatives such as 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.) , pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10, 11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, and polysilanes. Polycarbonate, styrene derivatives, polyvinylcarbazole, polysilane, etc., which have the above-mentioned monomers in their side chains, are preferred as polymers, but they form the thin film necessary for producing light-emitting devices, allow holes to be injected from the anode, and further It is not particularly limited as long as it is a compound that can transport.

It is also known that the conductivity of organic semiconductors is strongly influenced by their doping. Such an organic semiconductor matrix material is composed of a compound with good electron donating properties or a compound with good electron accepting properties. For doping with electron donating substances, strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known. (For example, the literature "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)" and the literature "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by electron transfer processes in electron-donating base materials (hole-transporting materials). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. As matrix materials having hole transport properties, for example benzidine derivatives (TPD etc.) or starburst amine derivatives (TDATA etc.) or certain metal phthalocyanines (in particular zinc phthalocyanine (ZnPc) etc.) are known ( JP 2005-167175A).
The compound of the present invention may be used as a material for forming a hole injection layer or a material for forming a hole transport layer.

<Electron blocking layer in organic electroluminescent device>
An electron blocking layer may be provided between the hole injection/transport layer and the light emitting layer to prevent diffusion of electrons from the light emitting layer. A compound represented by any of the above formulas (H1), (H2), and (H3) can be used to form the electron blocking layer. The compound of the present invention may be used as a material for forming an electron blocking layer.

<Electron injection layer and electron transport layer in 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 electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport/injection materials, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer is a layer that is in charge of injecting electrons from the cathode and further transporting electrons, and it is desirable that the electron injection efficiency is high and that the injected electrons are efficiently transported. For this purpose, it is preferable that the material has high electron affinity, high electron mobility, excellent stability, and does not easily generate trapping impurities during production and use. However, when considering the transport balance of holes and electrons, if the role is to efficiently prevent holes from the anode from flowing to the cathode side without recombining, the electron transport capacity is not so great. Even if it is not high, it has the same effect of improving luminous efficiency as a material with high electron transport ability. Therefore, the electron injection/transport layer in this embodiment may also include the function of a layer that can efficiently block the movement of holes.

The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 may be a compound conventionally used as an electron transport compound in photoconductive materials, or a compound used in the electron injection layer and electron transport layer of an organic EL device. Any known compound may be selected and used.

Materials used for the electron transport layer or electron injection layer include compounds consisting of an aromatic ring or a heteroaromatic 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 pyrrole derivatives, fused ring derivatives thereof, and metal complexes having electron-accepting nitrogen. Specifically, fused ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes 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 can be used alone or in combination with different materials.

Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, and diphenylquinone derivatives. , perylene derivatives, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl) -1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazines derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazol-2-yl)benzene, etc.), benzoxazole derivatives, thiazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4' -(2,2':6'2"-terpyridinyl))benzene, etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives , pyrimidine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bisstyryl derivatives, silole derivatives and azoline derivatives.

Further, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

The above-mentioned materials can be used alone, but they can also be used in combination with different materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, quinolinol metal complexes , thiazole derivatives, benzothiazole derivatives, silole derivatives and azoline derivatives are preferred.

The compound of the present invention may be used as a material for forming an electron injection layer or a material for forming an electron transport layer.

[Reducing substances, others]
The electron transport layer or the electron injection layer may further contain a substance that can reduce the material forming the electron transport layer or the electron injection layer. A variety of substances can be used as this reducing substance as long as it has a certain reducing property, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, and alkali metals. 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 suitably used.

Preferred reducing substances include alkali metals such as Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), or Cs (work function: 1.95 eV), and Ca (work function: 2.3 eV). Examples include alkaline earth metals such as Sr (2.0 to 2.5 eV), Sr (2.0 to 2.5 eV), and Ba (2.52 eV), and substances with a work function of 2.9 eV or less are particularly preferred. Among these, more preferable reducing substances are alkali metals such as K, Rb, or Cs, still more preferably Rb or Cs, and most preferable is Cs. These alkali metals have 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 luminance of the organic EL element can be improved and the life of the organic EL element can be extended. Further, as a reducing substance with a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By including Cs, the reducing ability can be efficiently exhibited, and by adding it to the material forming the electron transport layer or the electron injection layer, the luminance of light emission and the longevity of the organic EL element can be improved.

<Cathode in organic electroluminescent device>
The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material 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 alloys, aluminum-lithium alloys such as lithium fluoride/aluminum), etc.) are preferred. In order to increase electron injection efficiency and improve device characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. In order to improve this point, a method is known in which, for example, the organic layer is doped with a trace amount of lithium, cesium, or magnesium to use a highly stable electrode. Other dopants that can also be used are inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. However, it is not limited to these.

Additionally, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys of these metals, as well as inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, and vinyl chloride, are used to protect the electrodes. A preferred example is to laminate a hydrocarbon polymer compound or the like. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

<Binders that may be used in each layer>
The above materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can be used alone to form each layer, but polyvinyl chloride, polycarbonate, Polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and curable resins such as silicone resins. be.

<Method for manufacturing organic electroluminescent device>
Each layer constituting an organic EL element is prepared by using a vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, inkjet method, spin coating method or casting method, coating method, etc. It can be formed by forming a thin film using a method. The thickness of each layer thus formed is not particularly limited and can be set appropriately depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillation type film thickness measuring device. When forming a thin film using an evaporation method, the evaporation conditions vary depending on the type of material, the intended crystal structure and association structure of the film, and so on. The deposition conditions are generally a boat heating temperature of +50 to +400°C, a vacuum level of 10 ^-6 to 10 ^-3 Pa, a deposition rate of 0.01 to 50 nm/sec, a substrate temperature of -150 to +300°C, and a film thickness of 2 nm to 5 μm. It is preferable to set it appropriately within a range.

Next, as an example of a method for producing an organic EL device, an organic EL device consisting of an anode/hole injection layer/hole transport layer/light emitting layer made of a host material and dopant material/electron transport layer/electron injection layer/cathode will be described. The manufacturing method will be explained. After a thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, thin films of a hole injection layer and a hole transport layer are formed on this anode. On top of this, a host material and a dopant material are co-deposited to form a thin film to form a light-emitting layer, an electron transport layer and an electron injection layer are formed on this light-emitting layer, and a thin film of a cathode material is further formed by vapor deposition or the like. By forming it and using it as a cathode, the desired organic EL element can be obtained. In addition, in the production of the above-mentioned organic EL element, it is also possible to reverse the production order and produce the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode in this order. It is.

When applying a direct current voltage to the organic EL element obtained in this way, it is sufficient to apply it with the anode as + polarity and the cathode as - polarity. Luminescence can be observed from the sides (anode or cathode, or both). This organic EL element also emits light when pulsed current or alternating current is applied. Note that the waveform of the applied alternating current may be arbitrary.

<Application examples of organic electroluminescent devices>
Further, the present invention can be applied to a display device equipped with an organic EL element or a lighting device equipped with an organic EL element.
A display device or a lighting device equipped with an organic EL element can be manufactured by a known method such as connecting the organic EL element according to this embodiment with a known drive device, and can be manufactured by a known method such as direct current drive, pulse drive, alternating current drive, etc. It can be driven using a known driving method as appropriate.

Examples of display devices include panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescent (EL) displays, etc. (Refer to the official gazette, Japanese Patent Application Laid-open No. 2004-281086, etc.). In addition, examples of display methods include matrix and/or segment methods. Note that matrix display and segment display may coexist in the same panel.

In a matrix, display pixels are arranged two-dimensionally in a grid or mosaic pattern, and characters or images are displayed as a collection of pixels. The shape and size of pixels are determined by the application. For example, rectangular pixels with sides of 300 μm or less are usually used to display images and characters on computers, monitors, and televisions, and in the case of large displays such as display panels, pixels with sides of mm order are 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 delta types and striped types. As a driving method for this matrix, either a line sequential driving method or an active matrix driving method may be used. Line sequential driving has the advantage of a simpler structure, but when considering operating characteristics, active matrix driving may be superior in some cases, so it is necessary to use it properly depending on the application.

In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is caused to emit light. Examples include time and temperature displays on digital clocks and thermometers, operating status displays on audio equipment and electromagnetic cookers, and panel displays on automobiles.

Examples of lighting devices include lighting devices for indoor lighting, backlights for liquid crystal display devices, etc. etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, watches, audio devices, automobile panels, display boards, signs, and the like. In particular, considering that it is difficult to reduce the thickness of liquid crystal display devices, especially backlights for personal computers where thinning is an issue, since conventional systems consist of fluorescent lamps and light guide plates, this embodiment A backlight using a light emitting element according to the above is characterized by being thin and lightweight.

4-2. Other Organic Devices The polycyclic aromatic compound according to the present invention can be used in the production of organic field effect transistors, organic thin film solar cells, etc. in addition to the organic electroluminescent devices described above.

An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and is provided with a gate electrode in addition to a source electrode and a 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 and drain electrodes can be arbitrarily blocked and the current can be controlled. Field-effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.

The structure of an organic field effect transistor is usually such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and a source electrode and a drain electrode are further provided in contact with the organic semiconductor active layer. A gate electrode may be provided with an insulating layer (dielectric layer) sandwiched therebetween. Examples of the device structure include the following structure.
(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 field effect transistor configured in this way is It can be applied as a pixel drive switching element for active matrix drive type liquid crystal displays and organic electroluminescent displays.

An 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 polycyclic aromatic compound according to 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 polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. The organic thin film solar cell may appropriately include a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, etc. in addition to the above. For the organic thin film solar cell, known materials used for organic thin film solar cells can be appropriately selected and used in combination.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis example (1): Synthesis of compound (11-1-1)

N ² ,N ⁶ -diphenyl-2,6-pyridinediamine (1.31 g, 5.0 mmol), 1-bromo-3-iodobenzene (1.40 mL, 11.0 mmol), sodium tert-butoxide (1.06 g , 11.0 mmol), bis(dibenzylideneacetone)palladium(0) (0.114 g, 0.125 mmol), 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene (0.144 g, 0.25 mmol) was added to o-xylene (25 mL) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 120° C. for 8 hours. The reaction solution was cooled to room temperature and passed through a silica gel short pass column (eluent/dichloromethane). After distilling off the solvent under reduced pressure, the crude product was subjected to a silica gel column (eluent/hexane:dichloromethane=2:1, 1:1, ethyl acetate). As a result, N ² ,N ⁶ -bis(3-bromophenyl)-N ² ,N ⁶ -diphenyl-2,6-pyridinediamine (2.01 g, yield 70%) was obtained as a white powder.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.22 (d, 2H), 7.02-7.068 (m, 4H), 7.10-7.14 (m, 8H), 7.18 (s, 2H), 7.25-7.30 (m , 5H)
¹³ C NMR (δppm in CDCl ₃ , 500 MHz); 106.0 (2C), 122.3 (1C), 124.5 (2C), 124.9 (2C), 126.7 (2C), 126.8 (4C), 128.6 (2C), 129.4 ( 4C), 130.0 (2C), 139.0 (2C), 145.2 (2C), 147.1 (2C), 157.2 (2C)

N ² ,N ⁶ -bis(3-bromophenyl)-N ² ,N ⁶ -diphenyl-2,6-pyridinediamine (0.286 g, 0.50 mmol), aniline (45.6 μL, 0.50 mmol), Tasha Libutoxysodium (0.105g, 1.1mmol), bis(dibenzylideneacetone)palladium(0) (11.4mg, 12.5μmol), 1,1'-bis(diphenylphosphino)ferrocene (13.9mg, 25.0 μmol) was added to toluene (2.5 mL) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 60° C. for 6 hours. After the reaction solution was cooled to room temperature, it was passed through a silica gel short pass column (eluent/dichloromethane). After distilling off the solvent under reduced pressure, the crude product was subjected to a silica gel column (eluent/hexane:dichloromethane=3:1). As a result, N ² -(3-bromophenyl)-N ² ,N ⁶ -diphenyl-N ⁶ -(3-phenylaminophenyl)-2,6-pyridinediamine (93.4 mg, yield 32%) was obtained as a white powder. ) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 5.56 (s, 1H), 6.19 (d, 1H), 6.25 (d, 1H), 6.68 (d, 1H), 6.80 (d, 2H), 6.88 ( t, 1H), 6.96-6.98 (m, 2H), 7.00 (d, 1H), 7.04 (t, 2H), 7.09-7.14 (m, 7H), 7.19-7.29 (m, 8H)
¹³ C NMR (δppm in CDCl ₃ , 500 MHz); 105.7 (1C), 106.0 (1C), 113.5 (1C), 116.0 (1C), 117.6 (2C), 119.1 (1C), 120.8 (1C), 122.2 ( 1C), 124.2 (1C+1C), 124.7 (1C), 126.3 (2C+1C), 126.6 (2C), 128.3 (1C), 128.9 (2C), 129.2 (2C), 129.3 (2C), 129.7 (1C) ), 129.9 (1C), 138.7 (1C), 142.8 (1C), 143.7 (1C), 145.5 (1C+1C), 146.6 (1C), 147.4 (1C), 157.1 (1C), 157.5 (1C)

N ² -(3-bromophenyl)-N ² ,N ⁶ -diphenyl-N ⁶ -(3-phenylaminophenyl)-2,6-pyridinediamine (0.875 g, 1.5 mmol) was added at room temperature under a nitrogen atmosphere. A solution of sodium tert-butoxy (0.173 g, 1.8 mmol), bis(dibenzylideneacetone) palladium(0) (34.3 mg, 37.5 μmol), Libutylphosphonium tetrafluoroborate (21.8 mg, 75.0 μmol) was added dropwise to a solution of o-xylene (25 mL) at room temperature under a nitrogen atmosphere while heating and stirring for 4 hours under reflux conditions. I did it. The reaction solution was cooled to room temperature and passed through a silica gel short pass column (eluent/dichloromethane, ethyl acetate). After distilling off the solvent under reduced pressure, the crude product was subjected to a silica gel column (eluent/hexane:toluene=1:1, dichloromethane, hexane:dichloromethane=1:1, dichloromethane). As a result, the compound (11-1-1), 2,4,6-triphenyl-2,4,6-triaza-1(2,6)-pyridina-3,5(1,3)- 0.550 g of dibenzenacyclohexaphane (yield 73%) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.37 (d, 2H), 6.54 (dd, 2H), 6.88 (dd, 2H), 7.02 (t, 2H), 7.09 (t, 1H), 7.18 ( t, 2H), 7.24 (t, 1H), 7.33-7.36 (m, 6H), 7.39 (t, 4H), 7.46 (d, 2H), 7.67 (t, 2H)
¹³ C NMR (δppm in CDCl ₃ , 500 MHz); 106.0 (2C), 117.8 (2C), 119.4 (2C), 123.2 (1C), 124.1 (2C), 124.4 (2C), 124.9 (4C), 126.4 ( 2C), 128.0 (2C), 129.3 (2C), 129.5 (4C), 138.4 (1C), 144.3 (2C+2C), 145.1 (1C), 147.7(2C), 156.0 (2C)

Synthesis example (2):
Compound (1-2-1), 3c-bromo-4,8,12-triphenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -phenylboradibenzo [cd, mn] Synthesis of pyrene

Compound (11-1-1), 2,4,6-triphenyl-2,4,6-triaza-1(2,6)-pyridina-3,5(1,3)-dibenzenacyclohexaphane (50. 3 g, 0.10 mmol) and boron tribromide (11.4 μL, 0.12 mmol) were added to o-dichlorobenzene (1.0 mL) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred under reflux conditions for 5 hours. Ta. After cooling the reaction solution to room temperature, the solvent was distilled off and the crude product was washed with hexane to give compound (1-2-1) 3c-bromo-4,8,12-tri as a yellow powder. Phenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -phenylboradibenzo[cd,mn]pyrene (41.2 mg, yield 70%) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.05 (d, 2H), 6.17 (d, 2H), 6.45 (d, 2H), 7.41-7.45 (m, 4H), 7.59 (d, 4H), 7.64-7.81 (m, 10H)
¹³ C NMR (δppm in CDCl ₃ ,500 MHz); 103.9 (2C), 106.4 (2C), 111.0 (2C), 129.2 (4C), 129.5 (2C), 129.7 (1C), 130.7 (2C), 131.4 ( The NMR signal of the carbon α to the boron was not observed.

Synthesis example (3):
Compound (1-1-1), 3c,4,8,12-tetraphenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -phenylboradibenzo[cd,mn]pyrene synthesis

Compound (11-1-1), 2,4,6-triphenyl-2,4,6-triaza-1(2,6)-pyridina-3,5(1,3)-dibenzenacyclohexaphane (50. 3 g, 0.10 mmol) and boron tribromide (9.48 μL, 0.10 mmol) were added to o-dichlorobenzene (1.0 mL) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred under reflux conditions for 5 hours. Ta. After the reaction solution was cooled to room temperature, it was added to a solution of phenyl Grignard reagent (0.283 mL, 0.30 mmol) at room temperature. After stirring at room temperature for 1 hour, methanol was added and the mixture was passed through a Florisil short pass column (eluent/dichloromethane). After distilling off the solvent under reduced pressure, the crude product was washed with hexane and acetonitrile to obtain the compound (1-1-1), 3c,4,8,12-tetraphenyl-4H,8H, as a white powder. 12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -phenylboradibenzo[cd,mn]pyrene (48.3 mg, yield 82%) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 5.70 (d, 2H), 5.76 (d, 2H), 6.06 (d, 2H), 6.72 (t, 2H), 7.07-7.10 (m, 2H), 7.19 (t, 2H), 7.29-7.32 (m, 6H), 7.41-7.51 (m, 5H), 7.56-7.61 (m, 6H)
¹³ C NMR (δppm in CDCl ₃ ,500 MHz); 102.0 (2C), 106.9 (2C), 109.5 (2C),124.9 (1C), 126.0 (2C), 127.3 (2C), 127.6 (1C),128.9 ( 2C), 130.4 (2C+4C), 130.7 (2C), 130.8 (4C), 131.3 (2C), 139.5 (1C), 140.3 (2C), 142.3 (2C), 142.6 (1C), 145.4 (2C), 151.7 (2C); The NMR signal of the carbon α to the boron was not observed.

Synthesis example (4):
Compound (1-3-1), 4,8,12-triphenyl-4H,8H,12H-3b,4,8,12-tetraaza-3c-boradibenzo[cd,mn]pyrene-3c-ium-trifluoromethane Synthesis of sulfonates

Compound (11-2-1), 3c-bromo-4,8,12-triphenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -phenylboradibenzo [cd, mn] Dichloromethane (1.0 mL) was added to pyrene (29.6 mg, 50.0 μmol) and silver trifluoromethanesulfonate (12.9 mg, 50.0 μmol) at room temperature under a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours. . After distilling off the solvent under reduced pressure, the obtained crude product was washed with toluene and hexane to obtain compound (1-3-1), 4,8,12-triphenyl-4H, 8H, 12H as a yellow solid. -3b,4,8,12-tetraaza-3c-boradibenzo[cd,mn]pyrene-3c-ium-trifluoromethanesulfonate (25.8 mg, yield 78%) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.04 (d, 2H), 6.13 (d, 2H), 6.44 (d, 2H),7.40-7.44 (m, 4H),7.56 (d, 4H), 7.64-7.69 (m, 4H),7.72-7.78 (m, 6H)
¹³ C NMR (δppm in CDCl ₃ , 500 MHz); 103.9 (2C), 106.4 (2C), 110.9 (2C), 129.2 (4C), 129.5 (2C), 129.7 (1C), 130.7 (2C), 131.4 ( The NMR signal of the carbon α to the boron was not observed.

Synthesis example (5):
Compound (1-4-1), 3c-pentamethylcyclopentadienyl-4,8,12-triphenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -boradibenzo [cd , mn] Synthesis of pyrene

Compound (11-1-1), 2,4,6-triphenyl-2,4,6-triaza-1(2,6)-pyridina-3,5(1,3)-dibenzenacyclohexaphane (0. After adding butyllithium (0.375 mL, 0.6 mmol) to 251 g, 0.50 mmol) and tert-butylbenzene (2.5 mL) at -45 °C under a nitrogen atmosphere, the mixture was heated and stirred at 60 °C for 1 hour. Ta. After the reaction solution was cooled to room temperature, the solvent was distilled off. Then, after adding dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (0.398 mg, 0.50 mmol), sodium acetate (82.1 mg, 1.0 mmol), and tetrahydrofuran (2.5 mL), The mixture was heated and stirred at ℃ for 8 hours. After the reaction solution was cooled to room temperature, it was passed through a Celite short pass column (eluent/dichloromethane). After distilling off the solvent under reduced pressure, the crude product was recrystallized using toluene and washed with hexane and methanol to obtain compound (1-4-1) and 3c-pentamethylcyclo as a yellow powder. Pentadienyl-4,8,12-triphenyl-4H,8H,12H-3bλ ⁴ ,4,8,12-tetraaza-3cλ ⁴ -boradibenzo[cd,mn]pyrene (41.4 mg, yield 10%) I got it.

¹ H NMR (δppm in CDCl _3,500 MHz); 1.53 (s, 15H), 5.89 (d, 2H), 6.03 (d, 2H),6.66 (t, 2H),6.69 (t, 1H),6.96 ( HRMS (ESI ) m/z [M+Na] ⁺ calcd for C ₄₅ H ₃₉ IrN ₄ Na 851.2702; observed 851.2706.

Synthesis example (6): Synthesis of compound (11-2-1)

3-chloro-N-phenylaniline (2.04 g, 10.0 mmol), 2,6-dibromopyridine (3.55 g, 15.0 mmol), sodium tert-butoxy (2.40 g, 25.0 mmol), bis( dibenzylideneacetone) palladium (0) (0.366 g, 40.0 μmol), 1,1'-bis(diphenylphosphino)ferrocene (0.463 g, 80.0 μmol) were added toluene (50 mL) at room temperature under a nitrogen atmosphere. ) was added thereto, and the mixture was heated and stirred at room temperature for 8 hours. The reaction solution was passed through a silica gel short pass column (eluent/toluene), and then the solvent was distilled off under reduced pressure. Thereafter, the crude product was subjected to a silica gel column (eluent/hexane:toluene=8:1, 4:1, toluene). As a result, 6-bromo-N-(3-chlorophenyl)-N-phenylpyridin-2-amine (2.37 g, yield 66%) was obtained as a white solid.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.56 (d, 1H), 6.97 (d, 1H), 7.07-7.11 (m, 2H), 7.15 (t, 1H), 7.18 (d, 2H), 7.22 (t, 1H), 7.23 (t, 1H), 7.27 (t, 1H), 7.37 (t, 2H)
¹³ C NMR (δppm in CDCl _3,500 MHz); 111.6 (1C), 119.9 (1C), 123.9 (1C),124.7 (1C), 125.8 (1C), 125.9 (1C), 127.0 (2C),129.8 ( 2C), 130.0 (1C), 134.6 (1C), 139.4 (1C), 139.9 (1C), 144.7 (1C), 146.4 (1C), 158.2 (1C)

6-bromo-N-(3-chlorophenyl)-N-phenylpyridin-2-amine (1.80 g, 5.0 mmol), N ² ,N ⁶ -diphenyl-2,6-pyridinediamine (1.57 g, 6 .0 mmol), tert-butoxysodium (1.20 g, 12.5 mmol), bis(dibenzylideneacetone)palladium(0) (91.6 mg, 0.100 mmol), 4,5-bis(diphenylphosphino)-9 Toluene (25 mL) was added to ,9-dimethylxanthene (0.116 g, 0.200 mmol) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 80° C. for 24 hours. After the reaction solution was cooled to room temperature, it was passed through a silica gel short pass column (eluent/dichloromethane), and the solvent was distilled off under reduced pressure. Thereafter, sublimation purification was performed using the crude product. As a result, N ² -(3-chlorophenyl)-N ² ,N ⁶ -diphenyl-N ⁶ -(6-(phenylamino)pyridin-2-yl)pyridine-2,5-diamine (0.864 g) was obtained as a white solid. , yield 32%).

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 5.56 (s, 1H),6.28 (d, 1H), 6.30 (s, 1H), 6.33 (d, 1H),6.47 (d, 1H),6.50 ( d, 1H),6.89 (t, 1H),6.95 (d, 1H),6.99 (d, 1H),7.02-7.05 (m, 7H), 7.19-7.28 (m, 7H),7.31 (t, 1H) , 7.34 (t, 2H)
¹³ C NMR (δppm in CDCl ₃ , 500 MHz); 102.1 (1C), 107.0 (1C), 107.1 (1C), 108.8(1C), 118.9 (2C), 121.5 (1C), 123.5 (1C), 123.8 ( 1C), 124.9 (1C),125.2 (1C), 125.5 (1C), 126.9 (2C), 128.0 (2C), 128.8 (2C), 129.2 (2C), 129.4 (2C), 129.6 (1C), 134.1 ( 1C), 138.5 (1C), 138.7 (1C), 140.7 (1C), 145.0 (1C), 145.3 (1C), 147.0 (1C), 154.2 (1C), 156.4 (1C), 156.7 (1C), 157.1 ( 1C)

N ² -(3-chlorophenyl)-N ² ,N ⁶ -diphenyl-N ⁶ -(6-(phenylamino)pyridin-2-yl)pyridine-2,5-diamine (54.0 mg, 0.10 mmol), Sodium tert-butoxy (9.61 mg, 0.10 mmol), bis(dibenzylideneacetone)palladium(0) (1.83 mg, 2.00 μmol), 2,2'-bis(diphenylphosphino)-1,1' - O-xylene (2.0 mL) was added to binaphthyl (2.49 mg, 4.00 μmol) at room temperature under a nitrogen atmosphere, and the mixture was heated at 60°C for 1 hour, at 90°C for 1 hour, at 120°C for 8 hours, and at 140°C. The mixture was heated and stirred for 8 hours. After the reaction solution was cooled to room temperature, it was passed through a silica gel short pass column (eluent/dichloromethane, ethyl acetate), and the solvent was distilled off under reduced pressure. Thereafter, the crude product was subjected to gel permeation chromatography (eluent/dichloroethane), and then the solvent was distilled off under reduced pressure. Thereafter, a silica gel column (eluent/dichloromethane:hexane=4:1, dichloromethane, ethyl acetate) was applied, followed by washing with hexane. As a result, the compound (11-2-1), 2,4,6-triphenyl-2,4,6-triaza-1,3(2,6)-dipyridina-5(1,3)- Benzenacyclohexaphane (10.1 mg, yield 20%) was obtained.

¹ H NMR (δppm in CDCl ₃ , 500 MHz); 6.03 (d, 2H), 6.52 (d, 2H), 6.74 (dd, 2H), 7.01 (t, 1H), 7.11 (t, 2H),7.24 ( t, 2H),7.24-7.38 (m, 9H), 7.44 (d, 2H),7.48 (t, 2H),8.48 (t, 1H)
¹³ C NMR (δppm in CDCl ₃ ,500 MHz); 108.4 (2C), 108.8 (2C), 120.3 (2C),123.1 (4C), 123.3 (2C), 127.1 (2C), 128.4 (1C),129.3 ( 2C), 129.5 (4C), 130.2 (2C), 130.8 (4C), 138.6 (1C), 142.3 (1C), 143.5 (1C), 144.2 (2C), 144.8 (2C)

By appropriately changing the raw material compounds, other compounds of the present invention can be synthesized by a method similar to the above-mentioned synthesis example.

Next, evaluation of basic physical properties of the compound of the present invention and production and evaluation of an organic EL device using the compound of the present invention will be described.

<Evaluation of basic physical properties>
Sample preparation
When evaluating the absorption characteristics and emission characteristics (fluorescence and phosphorescence) of a compound to be evaluated, there are cases where the compound to be evaluated is dissolved in a solvent and evaluated in the solvent, or evaluated in a thin film state. Furthermore, when evaluating in a thin film state, depending on the mode of use of the compound to be evaluated in an organic EL element, there are cases where only the compound to be evaluated is made into a thin film and evaluated, and cases where the compound to be evaluated is dispersed in an appropriate matrix material. In some cases, the film may be made into a thin film for evaluation. As the matrix material, commercially available PMMA (polymethyl methacrylate) or the like can be used. A thin film sample dispersed in PMMA can be prepared by, for example, dissolving PMMA and the compound to be evaluated in toluene, and then forming a thin film on a transparent support substrate (10 mm x 10 mm) made of quartz using a spin coating method. I can do it. Further, a method for producing a thin film sample when the matrix material is the host material will be described below. A transparent support substrate made of quartz (10 mm x 10 mm x 1.0 mm) was fixed to a substrate holder of a commercially available evaporation apparatus (manufactured by Showa Shinku Co., Ltd.), and a molybdenum evaporation boat containing a host material and a dopant material were placed. Attach a molybdenum vapor deposition boat. Next, the pressure in the vacuum chamber is reduced to 5×10 ^-4 Pa, and the evaporation boat containing the host material and the evaporation boat containing the dopant material are simultaneously heated to achieve an appropriate film thickness and the host material is evaporated to an appropriate thickness. A mixed thin film of the material and the dopant material is formed. The deposition rate is controlled according to a set weight ratio of host material and dopant material.

Evaluation of Absorption Characteristics and Luminescent Characteristics The absorption spectra of the samples were measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-2600). Further, the fluorescence spectrum or phosphorescence spectrum of the sample was measured using a spectrofluorophotometer (manufactured by Hitachi High-Tech Corporation, F-7000). For measurement of fluorescence spectra, photoluminescence was measured at room temperature with excitation at an appropriate excitation wavelength. The phosphorescence spectrum was measured while the sample was immersed in liquid nitrogen (temperature 77 K) using an attached cooling unit. To observe the phosphorescence spectrum, an optical chopper was used to adjust the delay time from excitation light irradiation to the start of measurement. The samples were excited at the appropriate excitation wavelength and photoluminescence was measured.

Evaluation of Delayed Fluorescence Fluorescence lifetime is measured at 300K using a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C11367-01). Observe components with fast and slow fluorescence lifetimes at the maximum emission wavelength measured at an appropriate excitation wavelength. In fluorescence lifetime measurements at room temperature of general organic EL materials that emit fluorescence, slow components involving triplet components derived from phosphorescence are rarely observed due to the deactivation of triplet components due to heat. . If a slow component is observed in the compound to be evaluated, this indicates that triplet energy with a long excitation lifetime is transferred to singlet energy due to thermal activation and observed as delayed fluorescence.

<Evaluation of organic EL elements>
The compounds of the present invention are characterized by a suitable bandgap (Eg), high triplet excitation energy ( _ET ) and small ΔE _ST (energy difference between triplet excited state (T1) and singlet excited state (S1)). Therefore, it can be expected to be applied particularly to light-emitting layers and charge transport layers.

Structure of Organic EL Device The structure of an organic EL device using the compound of the present invention includes, for example, the following structure A and structure B.

(Element configuration A)
Table 1 below shows an example of the constituent materials for each layer as a reference. Further improvement in properties is expected by replacing at least one of the hole transport layer material, electron blocking layer material, light emitting layer host material, light emitting layer dopant material, or electron transport layer material in this configuration with the compound of the present invention. can. Note that the thickness and constituent materials of each layer can be changed as appropriate depending on the basic physical properties of the compound of the present invention.

In Table 1, "HI" (hole injection layer material) is N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, and "HT" (hole transport layer material) is 4,4',4"-tris(N-carbazolyl)triphenylamine, "EB" (electron blocking layer material) is 1,3-bis(N-carbazolyl)benzene, "EM-H" ( The light-emitting layer host material) is 3,3'-bis(N-carbazolyl)-1,1'-biphenyl, and "Firpic" (the light-emitting layer dopant material) is bis[2-(4,6-difluorophenyl)pyridinato. -N,C ² ](picolinato)iridium(III), and "ET" (electron transport layer material) is diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide. The chemical structure is shown below.

(Element configuration B)
An example of the constituent materials for each layer as a reference is shown in Table 2 below. By replacing at least one of the material of the hole transport layer 1, the material of the hole transport layer 2, the host material of the light emitting layer, the dopant material of the light emitting layer, or the material of the electron transport layer in this structure, the compound of the present invention can be used. It is expected that the characteristics will be improved. Note that the thickness and constituent materials of each layer can be changed as appropriate depending on the basic physical properties of the compound of the present invention.

In Table 2, "HI" (hole injection layer material) is N ⁴ ,N ^4' -diphenyl-N ⁴ ,N ^4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1 '-biphenyl]-4,4'-diamine, and "HAT-CN" (hole injection layer material) is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile, and "HT -1'' (hole transport layer material) is N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3- yl)phenyl)-9H-fluoren-2-amine, and "HT-2" (hole transport layer material) is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl )-[1,1':4',1"-terphenyl]-4-amine, and "EM-H" (emissive layer host material) is 9-phenyl-10-(4-phenylnaphthalene-1- "BD1" (emissive layer dopant material) is 2,12-di-t-butyl-5,9-bis(4-(t-butyl)phenyl)-7-methyl-5,9- dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene, and "ET" (electron transport layer material) is 4,4'-((2-phenylanthracene-9,10- diyl)bis(4,1-phenylene))dipyridine. The chemical structure is shown below along with "Liq".

Manufacturing of organic EL device A method for manufacturing device configuration A will be described below.
A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.), in which ITO was formed into a 100 nm thick film by sputtering and polished to 50 nm, was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI (hole injection layer material), HT (hole transport layer material), EB (electron blocking layer material), A molybdenum deposition boat containing EM-H (host material), Firpic (dopant material), ET (electron transport layer material), and LiF (electron injection layer material), and a tungsten deposition boat containing aluminum. Installing.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The pressure in the vacuum chamber is reduced to 5×10 ⁻⁴ Pa, and first, HI is heated and evaporated to a thickness of 40 nm to form a hole injection layer. Next, HT is heated and deposited to a thickness of 15 nm to form a hole transport layer. Next, an electron blocking layer is formed by heating EB and depositing it to a thickness of 15 nm. Next, EM-H and Firpic (dopant material) are simultaneously heated and deposited to a thickness of 30 nm to form a light-emitting layer. The deposition rate is adjusted so that the weight ratio of EM-H to Firpic is approximately 95:5. Next, an electron transport layer was formed by heating the ET and depositing the film to a thickness of 40 nm. The deposition rate of each layer is 0.01 to 1 nm/sec.

Thereafter, LiF is heated and deposited to a thickness of 1 nm at a deposition rate of 0.01 to 0.1 nm/sec, and then aluminum is heated and deposited to a thickness of 100 nm to form a cathode. Then, an organic EL element is obtained. At this time, the aluminum deposition rate is adjusted to 1 nm to 10 nm/sec.

Element configuration B can also be manufactured by optimizing conditions in the same manner as element configuration A.

Evaluation items and evaluation methods Evaluation items include drive voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), maximum wavelength of emission spectrum (nm), and half-width ( nm) etc. For these evaluation items, for example, values at the time of light emission of 10 cd/m ² can be used.

There are two types of quantum efficiency for light-emitting devices: internal quantum efficiency and external quantum efficiency. Internal quantum efficiency refers to the state in which external energy injected as electrons (or holes) into the light-emitting layer of a light-emitting device is converted purely into photons. It shows the percentage of On the other hand, external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and some of the photons generated in the light-emitting layer are absorbed or continue to be reflected inside the light-emitting element. Since the light is not emitted to the outside of the light emitting device, the external quantum efficiency is lower than the internal quantum efficiency.

The method for measuring spectral radiance (emission spectrum) and external quantum efficiency is as follows. Using a voltage/current generator R6144 manufactured by Advantest Co., Ltd., a voltage such that the luminance of the device becomes 10 cd/m ² is applied to cause the device to emit light. Spectral radiance in the visible light region is measured in the direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light-emitting surface is a completely diffusing surface, the number of photons at each wavelength is obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying it by π. Next, the number of photons is integrated over the entire observed wavelength range to obtain the total number of photons emitted from the element. 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. Further, the half-width of the emission spectrum is determined as the width between the upper and lower wavelengths at which the intensity is 50%, centering on the maximum emission wavelength.

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 (17)

A complex which is a polycyclic aromatic compound represented by the following formula ( 1') or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (1').
(In formula (1'),
Z ^a each independently represents C-R ^a or N,
R ^a is each independently hydrogen, aryl optionally substituted with a second substituent , heteroaryl optionally substituted with a second substituent, or optionally substituted with a second substituent. good diarylamino, diheteroarylamino optionally substituted with a second substituent , arylheteroarylamino optionally substituted with a second substituent , optionally substituted with a second substituent Diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl optionally substituted with a second substituent , cyclo optionally substituted with a second substituent Alkyl, alkoxy optionally substituted with a second substituent , aryloxy optionally substituted with a second substituent , or silyl optionally substituted with a second substituent , and the same ring R ^a substituted for two adjacent Z ^a may be bonded to each other to form an aryl ring, a heteroaryl ring, or a cycloalkyl ring, and at least one hydrogen in the formed ring is diarylamino or diaryl. Optionally substituted with boryl (two aryls may be bonded via a single bond or a linking group),
The second substituent is selected from the group consisting of aryl, heteroaryl and alkyl, and aryl and heteroaryl as the second substituent also include groups in which at least one hydrogen is replaced with aryl or alkyl. Re,
Y is boron coordinated with a monodentate ligand or iridium coordinated with a monodentate ligand ;
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl, or heteroaryl; R may be bonded to ring a, ring b and/or ring c through a linking group or a single bond,
Z is a carbon atom or a nitrogen atom,
At least one hydrogen in the compound or structure represented by formula (1') may be substituted with cyano, halogen, or deuterium. ) R ^a is each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms), or diarylboryl (however, each aryl has 6 to 12 carbon atoms). Aryl is an aryl having 6 to 12 carbon atoms, and two aryls may be bonded via a single bond or a linking group), and R ^a substituted on two adjacent Z ^a in the same ring. may be combined with each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring a, ring b, or ring c, and at least one hydrogen in the formed ring is , diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms) or diarylboryl (however, each aryl is an aryl having 6 to 12 carbon atoms, and two aryls are bonded via a single bond or a linking group). 2. The complex according to claim 1 , which is optionally substituted with 2. Y is MR ^x , M is boron or iridium, and R ^x is aryl, heteroaryl, alkyl, cycloalkyl, alkoxy, halogen, cyano, cyclopentadienyl or sulfonate. The complex described in. The complex according to claim 1, which is represented by one of the following formulas.
(In the formula, Ph is phenyl, OTf is trifluoromethanesulfonate, and Cp* is pentamethylcyclopentadienyl.) A raw material for producing a boron or iridium complex containing a polycyclic aromatic compound represented by the following formula (11') or a multimer of a polycyclic aromatic compound having multiple structures represented by the following formula (11') .
(In formula (11'),
Z ^a each independently represents C-R ^a or N,
R ^a is each independently hydrogen, aryl optionally substituted with a second substituent , heteroaryl optionally substituted with a second substituent, or optionally substituted with a second substituent. good diarylamino, diheteroarylamino optionally substituted with a second substituent , arylheteroarylamino optionally substituted with a second substituent , optionally substituted with a second substituent Diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl optionally substituted with a second substituent , cyclo optionally substituted with a second substituent Alkyl, alkoxy optionally substituted with a second substituent , aryloxy optionally substituted with a second substituent , or silyl optionally substituted with a second substituent , and the same ring R ^a substituted for two adjacent Z ^a may be bonded to each other to form an aryl ring, a heteroaryl ring, or a cycloalkyl ring, and at least one hydrogen in the formed ring is diarylamino or diaryl. Optionally substituted with boryl (two aryls may be bonded via a single bond or a linking group),
The second substituent is selected from the group consisting of aryl, heteroaryl and alkyl, and aryl and heteroaryl as the second substituent also include groups in which at least one hydrogen is replaced with aryl or alkyl. Re,
X ¹ , X ² and X ³ are each independently O, NR, provided that R in the NR is alkyl, cycloalkyl, aryl or heteroaryl; may be bonded to ring a, ring b and/or ring c through a linking group or a single bond,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11') may be substituted with cyano, halogen, or deuterium. ) In the formula (11'),
R ^a is each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms), or diarylboryl (however, each aryl has 6 to 12 carbon atoms). Aryl is an aryl having 6 to 12 carbon atoms, and two aryls may be bonded via a single bond or a linking group), and R ^a substituted on two adjacent Z ^a in the same ring. may be combined with each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring a, ring b, or ring c, and at least one hydrogen in the formed ring is , diarylamino (however, each aryl is an aryl having 6 to 12 carbon atoms) or diarylboryl (however, each aryl is an aryl having 6 to 12 carbon atoms, and two aryls are bonded via a single bond or a linking group). ) may be replaced with
The manufacturing raw material according to claim 5 . The manufacturing raw material according to claim 5 or 6 , wherein the complex is the complex according to any one of claims 1 to 4 . Coordination between the nitrogen of the a-ring of the polycyclic aromatic compound represented by formula (11) or the multimer of the polycyclic aromatic compound having multiple structures represented by formula (11) and boron or iridium. A method for producing a complex using the production raw material according to any one of claims 5 to 7, which comprises forming a bond. The manufacturing method according to claim 8, wherein the complex is the complex according to any one of claims 1 to 4 . An organic device material containing the complex according to any one of claims 1 to 4 . An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the complex according to any one of claims 1 to 4 . A pair of electrodes consisting of an anode and a cathode, a luminescent layer disposed between the pair of electrodes, and a complex disposed between the cathode and the luminescent layer, comprising the complex according to any one of claims 1 to 4. An organic electroluminescent device comprising an electron injection layer and/or an electron transport layer. A pair of electrodes consisting of an anode and a cathode, a luminescent layer disposed between the pair of electrodes, and a complex according to any one of claims 1 to 4 disposed between the anode and the luminescent layer. An organic electroluminescent device comprising a hole injection layer and/or a hole transport layer. A display device comprising the organic electroluminescent element according to any one of claims 11 to 13 . A lighting device comprising the organic electroluminescent element according to any one of claims 11 to 13 . A polycyclic aromatic compound represented by the following formula (11') or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (11').
(In formula (11'),
Z ^a each independently represents C-R ^a ,
R ^a is each independently hydrogen, aryl optionally substituted with a second substituent , heteroaryl optionally substituted with a second substituent, or optionally substituted with a second substituent. good diarylamino, diheteroarylamino optionally substituted with a second substituent , arylheteroarylamino optionally substituted with a second substituent , optionally substituted with a second substituent Diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl optionally substituted with a second substituent , cyclo optionally substituted with a second substituent Alkyl, alkoxy optionally substituted with a second substituent , aryloxy optionally substituted with a second substituent , or silyl optionally substituted with a second substituent , and the same ring R ^a substituted for two adjacent Z ^a may be bonded to each other to form an aryl ring, a heteroaryl ring, or a cycloalkyl ring, and at least one hydrogen in the formed ring is diarylamino or diaryl. Optionally substituted with boryl (two aryls may be bonded via a single bond or a linking group),
The second substituent is selected from the group consisting of aryl, heteroaryl and alkyl, and aryl and heteroaryl as the second substituent also include groups in which at least one hydrogen is replaced with aryl or alkyl. Re,
X ¹ , X ² and X ³ are each independently O or NR, provided that R in NR is alkyl, cycloalkyl, aryl or heteroaryl,
Z ^X is CH or N,
At least one hydrogen in the compound or structure represented by formula (11') may be substituted with cyano, halogen, or deuterium. ) A polycyclic aromatic compound represented by any of the following formulas.