WO2017118155A1

WO2017118155A1 - Organic optoelectronic material and use thereof

Info

Publication number: WO2017118155A1
Application number: PCT/CN2016/102854
Authority: WO
Inventors: 潘君友; 黄宏
Original assignee: 广州华睿光电材料有限公司
Priority date: 2016-01-07
Filing date: 2016-10-21
Publication date: 2017-07-13
Also published as: CN108137610B; CN108137610A

Abstract

The present invention relates to an organic optoelectronic material and a use thereof. The organic optoelectronic material comprises an organic compound having a characteristic structure represented by formula (1). The organic compound has a relatively small ΔE(S₁-T₁) and thus has a good thermally activated delayed fluorescence, imparting an OLED device with high efficiency and increased longevity. Synthesis of the compound is relatively simple and low in cost, offering great potential and a wide scope of application. The present invention also relates to a mixture, a composition (printing ink) and an organic electronic device, particularly an electroluminescent device, comprising the organic compound.

Description

Organic photoelectric material and use thereof

Technical field

The invention relates to the field of organic photoelectric materials, in particular to an organic compound having thermal excitation delayed fluorescence characteristics, a composition thereof, a mixture thereof and the use thereof in an organic electronic device, particularly in an organic electroluminescent device. . The invention further relates to an organic electronic device comprising such a compound, in particular an electroluminescent device, and its use in displays and illumination devices.

Background technique

The diversity and synthesizable nature of organic electroluminescent materials have laid a solid foundation for the realization of large-area new display devices. In order to improve the luminous efficiency of organic light emitting diodes (OLEDs), fluorescent and phosphorescent based luminescent material systems have been developed. OLEDs using fluorescent materials have high reliability, but their internal electroluminescence quantum efficiency is limited to 25% under electrical excitation, because the branch ratio of the singlet excited state and the triplet excited state of excitons is 1. :3. In contrast, OLEDs using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency. However, there is a significant problem with phosphorescent OLEDs, that is, the Roll-off effect, that is, the luminous efficiency rapidly decreases with increasing current or brightness, which is particularly disadvantageous for high brightness applications.

So far, phosphorescent materials with practical use value are rhodium and platinum complexes, which are rare and expensive, and the synthesis of complexes is complicated, so the cost is also quite high. In order to overcome the rarity and high cost of the raw materials of rhodium and platinum complexes, and the complexity of their synthesis, Adachi proposed the concept of reverse intersystem crossing, which can be achieved by using organic compounds, ie without using metal complexes. High efficiency compared to phosphorescent OLEDs. This concept has been achieved through a combination of materials such as: 1) using a composite exciplex, see Adachi et al, Nature Photonics, Vol 6, p 253 (2012); 2) using thermally excited delayed fluorescence (TADF) materials. See Adachi et al., Nature, Vol 492, 234, (2012). However, most of the existing organic compounds with TADF are connected by electron donating (Donor) and electron-deficient or acceptor groups, resulting in complete distribution of the highest occupied orbit (HOMO) and the lowest unoccupied orbital (LUMO) electron cloud. Separation and reduction of the energy level difference (ΔE(S ₁ -T ₁ )) between the singlet state (S ₁ ) and the triplet state (T ₁ ) of the organic compound have an adverse effect on luminous efficiency and stability. So far, a series of red and green TADF materials have been developed to achieve relatively high luminous efficiency, but blue-light TADF luminescent materials are lacking, and the performance of OLED devices of all TADF materials, especially the life expectancy is still certain. difference.

Therefore, the prior art, especially the TADF material solution, has yet to be improved and developed.

Summary of the invention

Based on this, it is necessary to provide an organic compound, which aims to solve the problems of high cost, high efficiency, low roll-off and short life of the existing electrophosphorescent luminescent material, and to solve the low fluorescence quantum yield of the TADF organic luminescent material. The problem of short life.

An organic compound having the structural features shown in formula (1):

Wherein the dotted line in the structural formula represents a bond of an adjacent monomer in the organic compound;

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ or Ar _{7 are the} same or different and are selected from aromatic, heteroaromatic or non-aromatic ring systems having 2 to 40 carbon atoms, and are One or more R ₁ substituted or unsubstituted, and R ₁ may be the same or different when it occurs multiple times;

R _{1 is selected} from H; D; a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group; a branched or cyclic alkyl group having 3 to 20 C atoms; An oxy group, a thioalkoxy group or a silyl group; a substituted keto group having 1 to 20 C atoms; an alkoxycarbonyl group having 2 to 20 C atoms; and an aromatic having 2 to 10 carbon atoms Or heteroaryl; aryloxycarbonyl having 7 to 20 C atoms; cyano; carbamoyl; haloformyl; formyl; isocyano; isocyanate; thiocyanate; isothiocyanate an ester group; a hydroxyl group; _{nitro; CF 3; Cl; Br;} F; cross-linking group; having 5 to 40 ring atoms, a substituted or unsubstituted aromatic or heteroaromatic ring system; having 5 ~ 40 ring atoms, an aryloxy group or heteroaryloxy; wherein, among the plurality of R ₁ may be bonded to each other to form a monocyclic or polycyclic aliphatic or aromatic ring;

n is 1 or 2;

n ₁ is 0 or 1;

X, Y, Q, Z, U are single bonds or bridged groups which are bonded to Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ or Ar ₆ by a single bond or a double bond; wherein X, Y, At least one of Q is different from Z or U.

The organic compound according to the present invention facilitates the obtaining of thermally excited delayed fluorescent TADF characteristics. According to the principle of thermal excitation delayed fluorescent TADF material (see Adachi et al., Nature, Vol 492, 234, (2012)), when the Δ(S ₁ -T ₁ ) of the organic compound is sufficiently small, the triplet excitons of the organic compound can be Efficient illumination is achieved by reverse internal conversion to singlet excitons. In general, TADF materials are obtained by electron donating (Donor) to electron-deficient or acceptor groups, i.e., having a distinct DA structure.

The organic compound according to the present invention has a small ΔE(S ₁ -T ₁ ), and generally ΔE(S ₁ -T ₁ ) ≤0.30 eV, preferably ≤0.25 eV, more preferably ≤0.20 eV, more Preferably, it is ≤ 0.15 eV, preferably ≤ 0.10 eV.

Generally, the triplet level T ₁ of an organic compound depends on the substructure of the compound having the largest conjugated system. Generally, T ₁ decreases as the conjugated system increases. In certain preferred embodiments, the substructure of formula (1) has the largest conjugated system of formula (1a) below.

Preferably, in the case where the substituent is removed, the formula (1a) has no more than 36 ring atoms, preferably no more than 32, and most preferably no more than 28.

In further preferred embodiments, Formula (1a) in the case of removal of a substituent which T ₁ ≥2.0eV, Jiaoyou is T ₁ ≥2.2eV, more preferably it is T ₁ ≥2.4eV, still more preferably It is T ₁ ≥ 2.6 eV, and most preferably T ₁ ≥ 2.7 eV.

For the purpose of the present invention, the H atom or the bridging group CH ₂ group on the NH may be substituted by the R ¹ group, and R ₁ may further preferably be: (1) a C1 to C10 alkyl group, particularly preferably as follows. Group: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl Base, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl , ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, Propynyl, butynyl, pentynyl, hexynyl and octynyl; (2) C1-C10 alkoxy, particularly preferred are methoxy, ethoxy, n-propoxy, isopropoxy a group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) C2 to C10 aryl or heteroaryl, which may be one depending on the use Valence or divalent, in each case can also be replaced by the group R ₁ mentioned above And may be attached to the aromatic or heteroaromatic ring through any desired position, particularly preferably refers to the following groups: benzene, naphthalene, anthracene, phthalocyanine, indoline, quinone, fluorene, fluoranthene, butyl, Phenol, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, pyrene, isoindole, carbazole, pyridine , quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, pheno Oxazine, pyrazole, oxazole, imidazole, benzimidazole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, Anthraquinone, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzoxazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine , diazepine, 1,5-naphthyridine, carbazole, benzoporphyrin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3- Diazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine 1,2,3-triazine, tetrazole. 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, anthracene, pteridine, guanidinium and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.

In one embodiment, X, Y, Q, Z, U are the same or different and are selected from a single bond, a two bridged group or a triple bridged group;

The second bridging group is selected from:

Wherein R ₃ , R ₄ and R _{5 have} the same meanings as R ₁ . A group represented by the above structural unit represented by the dashed bonds _{_{_{Ar 1, Ar 2, Ar 3}}} , Ar 4 bond to.

The three bridging groups are selected from:

Wherein R ₄ , R ₅ and R _{6 have} the same meanings as R ₁ . The dotted line indicated by the above group indicates a bond bonded to the structural unit Ar ₁ or Ar ₂ or Ar ₅ and Ar ₃ or Ar ₄ or Ar ₆ .

In one embodiment, the two bridging groups are selected from:

The three bridging groups are selected from:

In one embodiment, the two bridging groups are selected from:

In one embodiment, X, Y, and Q are single bonds, and Z and U are both

In one embodiment, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ or Ar _{7 are the} same or different and are selected from aromatic or heteroaromatic rings having 2 to 20 carbon atoms. .

In one embodiment, Ar ₁ , Ar ₂ , Ar ₃ or Ar ₄ is an aromatic ring having 5 to 15 carbon atoms in the ring system; or

Ar ₁ , Ar ₂ , Ar ₃ or Ar ₄ is a heteroaromatic ring system having 2 to 15 carbon atoms and at least one hetero atom in the ring system, and the total number of the carbon atoms and hetero atoms is not less than 4 .

In one embodiment, the hetero atom is selected from the group consisting of Si, N, P, O, S, Ge.

In one embodiment, the hetero atom is selected from the group consisting of Si, N, P, O, S.

In one embodiment, Ar ₁ , Ar ₂ , Ar ₃ , Ar _{4 are the} same or different and are selected from:

Wherein X _{1 is selected} from CR ₆ or N;

Y _{1 is selected} from CR ₇ R ₈ , SiR ₉ R ₁₀ , NR ₁₁ or C(=O), S, or O;

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R _{11 have} the same meanings as R ₁ .

In one embodiment, Ar ₁ , Ar ₂ , Ar ₃ , and Ar _{4 are the} same or different and are selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyridine, perylene or thiophene.

In one embodiment, Ar ₅ , Ar ₆ , and Ar _{7 are the} same or different and are selected from aromatic or heteroaromatic rings having 2 to 40 carbon atoms.

In one _{_{embodiment, Ar 5, Ar 6, Ar}} 7 are optionally selected from: C2 to C40 aryl or heteroaryl group, depending on the use which can be monovalent or divalent and may in each case is a group R ₁ mentioned above and may be substituted with an aromatic or heteroaromatic ring bonded via any desired position of the aromatic, particularly preferably refers to the following group: benzene, naphthalene, pyrene, dihydro-pyrene, chrysene,茈, 丁, 戊, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, pyrene, isoindole , carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenanthrene Thiazide, phenoxazine, pyrazole, oxazole, imidazole, benzimidazole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, Naphthoxazole, anthraquinone, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzoxazine, pyrimidine, benzopyrimidine, quin Porphyrin, pyrazine, 1,5- Diazepine, carbazole, benzoporphyrin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole . 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, anthracene, pteridine, guanidinium and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.

In one embodiment, Ar ₅ , Ar ₆ , and Ar _{7 are the} same or different and are selected from:

n ₂ is 1 or 2 or 3 or 4.

In one embodiment, Ar ₅ , Ar ₆ , and Ar ₇ are each selected from:

In one embodiment, at least one of Ar ₅ , Ar ₆ , Ar ₇ includes an electron donating group, and/or at least one includes an electron withdrawing group.

In one embodiment, the electron donating group is selected from the group consisting of substituted or unsubstituted:

In one embodiment, the electron withdrawing group is selected from the group consisting of F, cyano or the following groups:

Where n ₃ is 1, 2, 3 or 4;

X ² -X ⁹ are optionally selected from CR or N, and at least one is N;

Z ₁ , Z ₂ , and Z ₃ are each selected from N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R). , P (= O) R, S, S = O, SO 2 or absent, but at least not without a;

R is optionally selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

Preferably, according to the organic compound of the formula (1), when the sub-structure of the formula (1a) has an electron-withdrawing property, at least one of Ar ₅ to Ar ₇ contains an electron-donating group, and more preferably Ar ₅ At least two of Ar- ₇ contain an electron donating group.

Examples of suitable substructures of the formula (1a) having electron-withdrawing properties are, but are not limited to:

According to the compound of the formula (1), when the substructure of the formula (1a) has an electron donating property, at least one of Ar ₅ to Ar ₇ contains an electron withdrawing group, and more preferably, Ar ₅ to Ar _{7 have} at least one. Both contain an electron withdrawing group.

Suitable examples of sub-structures of the general formula (1a) having electron-donating properties, but are not limited to:

In one embodiment, the organic compound has structural features as defined in formulas (2)-(5):

In one embodiment, the organic compound has the structural characteristics of formula (6)-(21):

In one embodiment, the organic compound has the following structural features:

In one embodiment, the organic compound has the structural features as shown in formula (6):

In one embodiment, the organic compound is selected from the group consisting of:

The present invention also provides a high molecular polymer comprising structural features of the organic compound in a repeating unit. In certain embodiments, the high polymer is a non-conjugated high polymer wherein the structural unit as shown in the general formula (1) is on the side chain. In another preferred embodiment, the high polymer is a conjugated high polymer.

The present invention also provides an organic photoelectric material comprising the organic compound or the high molecular polymer, and at least one organic functional material; the organic functional material is selected from a hole (also called a hole) injection or Transmission material (HIM/HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic host material (Host), singlet illuminant (fluorescent illuminant) ), a heavy illuminant (phosphorescent illuminant), an organic thermal excitation delayed fluorescent material (TADF material), particularly a luminescent organic metal complex, and an organic dye. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of which is hereby incorporated by reference. The organic functional material may be a small molecule and a high polymer material.

Preferably, the organic optoelectronic material comprises the organic compound or the high molecular polymer, and a phosphorescent emitter. The organic compound or the high molecular polymer described herein may be used as a host, and the phosphorescent phosphor weight percentage ≤ 30 wt%, preferably ≤ 25 wt%, more preferably ≤ 20 wt%.

Preferably, the organic optoelectronic material comprises the organic compound or the high molecular polymer, and a host material. The organic compound or the high molecular polymer described herein may be used as a light-emitting material in a weight percentage of ≤ 30% by weight, preferably ≤ 25% by weight, more preferably ≤ 20% by weight, most preferably ≤ 15% by weight.

Preferably, the organic optoelectronic material comprises the organic compound or the high molecular polymer, a phosphorescent emitter and a host material. The organic compound or the high molecular polymer described herein may be used as an auxiliary luminescent material, and its weight ratio to the phosphorescent emitter is from 1:2 to 2:1. Further preferably, the organic compound or the high molecular polymer has a T ₁ higher than the phosphorescent emitter.

In one embodiment, the organic optoelectronic material comprises the organic compound or the high molecular polymer, and another TADF material.

The subject material, phosphorescent material and TADF material are described in some detail below (but are not limited thereto).

(1) Body material (TripletHost):

The example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant. Examples of metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer, Its value is from 1 to the maximum coordination number of this metal; m+n is the maximum coordination number of this metal.

In a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms.

In a certain embodiment, M can be selected from Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, anthracene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, three Azole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine Anthracene, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, Anthraquinone, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopyridine, benzothienopyridine, thienopyridine, benzoselenopyridine and selenophene a dipyridine; a group containing a 2 to 10 ring structure, which may be the same or different types of a cyclic aromatic hydrocarbon group or an aromatic heterocyclic group And coupled to each other directly or through at least one of the following groups together; such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Among them, each Ar Further substituted, the substituents may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

R ¹ -R ⁷ may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aromatic when aryl or heteroaryl group, Ar ² are the same meaning as above ¹ and Ar; n is an integer from 0 to 20; X ¹ -X ⁸ is selected in CH or N; X ⁹ is selected from CR ¹ R ² or in NR ¹ .

Examples of suitable triplet host materials are listed below:

(2) Phosphorescent materials

Phosphorescent materials are also called triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In a preferred embodiment, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd or Pt being particularly preferred.

Preferentially, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene. A quinolinol derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from transition metal elements or lanthanides or actinides;

Ar ¹ may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Connection; Ar ² may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar ¹ and Ar ² are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group, each of which may be the same or different, being an ancillary ligand, preferably a bidentate chelate ligand. Preferred is a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1 or 2, preferably 0 or 1, in particular Priority is 0;

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, these metal complexes are coupled to a polymer by one or more locations, preferably It is through organic ligands.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2-(2-thienyl)pyridine derivative, a 2-(1-naphthyl)pyridine derivative, or 2-phenylquinoline derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

Ar1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Ar2 may be the same or different at each occurrence, and is a cyclic group containing at least one C atom through which a cyclic group is bonded to a metal; Ar1 and Ar2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand, preferably Monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0 ;

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005 /0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000) , 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124 , Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998, 245, US Pat. No. 6,824,895, US Pat. No. 7,029,766, US Pat. No. 6,835,469, US Pat. No. 6,030, 828, US Patent No. 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

(3) TADF materials

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. But phosphorescence The problems of expensive materials, poor material stability, and severe roll-off of device efficiency limit its application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, and secondly ΔEst < 0.2 eV, preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al. Chem. Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. .Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. Al.J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby incorporated by reference to The entire contents are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below:

The present invention also provides an organic photoelectric composition or ink comprising the organic compound or the high molecular polymer, and at least one organic solvent.

The viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.

In a preferred embodiment, the ink according to the invention has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; It is in the range of 25dyne/cm to 33dyne/cm.

In another preferred embodiment, the ink according to the invention has a viscosity of about 1 cps at an operating temperature or at 25 ° C. To the range of 100 cps; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps; preferably in the range of 4.0 cps to 20 cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink. The ink containing the organic compound or polymer according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used. In general, the composition according to the present invention comprises the organic compound or polymer of the present invention in a weight ratio of from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight. The range is more preferably in the range of 0.5% to 10% by weight, most preferably in the range of 1% to 5% by weight.

In some embodiments, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention. Solvent, or aromatic ether solvent.

Examples of organic solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-di Methylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, methylene Ethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, Dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl) Benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenyl Propyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetrahydrogen Naphthone, 2-tetralone, 2-(phenyl epoxy) tetrahydrogen Ketone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2 -methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone , 2-fluorenone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene , Butoxybenzene, Benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1- Propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethyletherether, 1,2,4-trimethoxybenzene , 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butyl anisole, Trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2- Naphthyl ether, pentyl ether c hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethyl Alcohol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; Ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, oleic acid Alkyl esters and the like.

Further, according to the ink of the present invention, the at least one solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.

In other embodiments, the ink further comprises another organic solvent. Examples of another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, Toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1 , 1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.

In a preferred embodiment, the organic optoelectronic composition according to the invention is a solution.

In another preferred embodiment, the organic optoelectronic composition according to the invention is a suspension.

The organic photoelectric composition in the embodiment of the present invention may comprise 0.01 to 20% by weight of the organic compound according to the present invention or a mixture thereof, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably 0.25 to 5 wt% of an organic compound or a mixture thereof.

The invention also provides the use of the organic compound or the high molecular polymer in an organic electronic device. In particular, as a use of a coating or printing ink in the preparation of an organic electronic device, the preparation method is particularly preferably a production method by printing or coating.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, inkjet and inkjet printing. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

The organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), especially OLEDs. In an embodiment of the invention, the organic compound is preferably used in a light-emitting layer of an OLED device.

The present invention also provides an organic electronic device comprising the organic compound and/or the high molecular polymer.

Typically, such an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above.

In one embodiment, the organic electronic device is an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, Organic spintronic devices, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode), particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.

In one embodiment, the organic electronic device includes a light emitting layer;

The light emitting layer includes the organic compound or the high molecular polymer.

In one embodiment, the luminescent layer further comprises a phosphorescent emitter and/or a host material.

In the above-mentioned organic electronic device, particularly an OLED, a substrate, an anode, at least one of the light-emitting layer, and a cathode are included.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF ₂ /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of each of which are hereby incorporated by reference.

In a preferred embodiment, the organic electronic device, the luminescent layer thereof, is prepared by the organic optoelectronic composition of the present invention.

The organic electronic device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The invention also provides for the use of the organic electronic device in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors, and the like.

The invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.

Compared with the prior art, the present invention has the following beneficial effects:

The organic compound of the present invention contains four aromatic ring or heteroaromatic ring conjugated units, and ΔE(S ₁ -T ₁ ) ≤0.30 eV, which facilitates the realization of thermal excitation delayed fluorescence luminescence (TADF). The organic compound according to the present invention can be used as a TADF luminescent material, and by blending with a suitable host material, it is easy to improve its luminous efficiency and lifetime as an electroluminescent device, and provides a manufacturing cost low, high efficiency, long life, and low rolling. A solution for falling light-emitting devices.

detailed description

The organic photoelectric material of the present invention and its use will be further described in detail below in conjunction with specific examples.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the subject material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.

In the present invention, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

In the present invention, an aromatic ring system or an aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system. A heteroaromatic or heteroaromatic group refers to a hydrocarbyl group (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units (<10%). Non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.

Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In certain embodiments of the invention, at least one of Ar ₁ -Ar ₄ comprises a non-aromatic ring system having from 2 to 20 carbon atoms which is unsubstituted or substituted with R ₁ .

For the purposes of the present invention, non-aromatic ring systems contain from 1 to 10, preferably from 1 to 3, carbon atoms in the ring system, and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or grouped R _{1 is} mono- or polysubstituted, the groups R ₁ may be the same or different in each occurrence, and may also contain one or more heteroatoms, preferably Si, N, P, O, S and/or Ge, in particular Preferred from Si, N, P, O and/or S. These may, for example, be cyclohexyl- or piperidine-like systems or ring-like octadiene ring systems. The term also applies to fused non-aromatic ring systems.

The organic compound according to the invention is a small molecular material.

The term "small molecule" as defined in the present invention refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. The molecular weight of the small molecule is ≤ 4000 g/mol, preferably ≤ 3000 g/mol, more preferably ≤ 2000 g/mol, most preferably ≤ 1500 g/mol.

The polymer, that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. In addition, in the present invention, the high polymer also includes a dendrimer. For the synthesis and application of the tree, see Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles. N. Moorefield, Fritz Vogtle.

Conjugated polymer (conjugated polymer) is a polymer whose main chain is mainly composed of a backbone atoms of sp C ² hybrid orbital, well-known examples are: polyacetylene, polyacetylene and poly (phenylene vinylene), the main The C atom on the chain can also be substituted by other non-C atoms, and is still considered a conjugated polymer when the sp ² hybrid on the backbone is interrupted by some natural defects. Further, in the present invention, the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

In particular, the solubility of the organic small molecule compound is ensured by the substituent R ₁ on the units of the formulae (1) to (21) and optionally on the unit additionally present. These substituents can also promote solubility if other substituents are present.

The structural units of the general formulae (1) to (21) are suitable for various functions in organic small molecule compounds depending on the substitution pattern. Therefore, they are preferably used as the main skeleton of the small molecule compound or as an illuminant. In particular, which substituents are particularly suitable for which functions are described by the substituents X and Y and Q. The substituent R ₁ has an influence on the electronic properties of the units of the general formulae (1) to (21).

The invention will now be described in connection with specific embodiments.

Example 1

15-(4,6-diphenyl-1,3,5-triazinyl-2-yl)-5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c :4,5-c']dicarbazole

4.98 g of a 250 ml three-necked flask, 10 mmol of 5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c']dicarbazole, 0.36 g, 15 mmol of hydrogenated Sodium, 100 ml of tetrahydrofuran, stirred under N ₂ atmosphere at room temperature for 30 min, 2.97 g, 11 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine was reacted at 60 ° C for 12 hours, TLC The progress of the reaction was followed and the reaction was terminated and cooled to room temperature. The reaction solution was poured into water, washed with sodium hydride, and suction filtered to give a solid product which was dissolved in dichloromethane to remove impurities. Recrystallization from toluene/ethanol gave the product solid powder 15-(4,6-diphenyl-1,3,5-triazinyl-2-yl)-5,10-diphenyl-10,15-di Hydrogen-5H-pyrrole [3,2-c:4,5-c'] oxazole 6.2 g. MS (ASAP) = 729.3.

Example 2

5,10-diphenyl-15-(4'-(11-phenylindole[3,2-b]carbazole-5(11H)-yl)-[1,1'-diphenyl] -4-yl)-10,15-dihydro-5H-pyrrole[3,2-c:4,5-c']dioxazole

4.75 g of a 250 ml three-necked flask, 10 mmol of 5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c']dicarbazole, 6.2 g, 11 mmol of 5- (4'-Bromo-[1,1'-diphenyl]-4-yl)-11-phenyl-5,11-dihydroindole [3,2-b]carbazole, 6.9 g, 50 mmol of carbonic acid potassium, 0.26g, 1mmol18- crown ethers -6,3.0g, 15mmol cuprous iodide and 150ml of o-dichlorobenzene, in N ₂ atmosphere, 160 ℃ reaction, TLC tracking progress of the reaction, completion of the reaction, cooled to room temperature. The reaction solution was poured into water, washed with K ₂ CO ₃ and then filtered to give a solid product which was washed with dichloromethane. Recrystallization from methylene chloride and ethanol gave the product 5,10-diphenyl-15-(4'-(11-phenylindole[3,2-b]carbazole-5(11H)-yl) -[1,1'-diphenyl]-4-yl)-10,15-dihydro-5H-pyrrole[3,2-c:4,5-c']dioxazole 8.0 g, MS ( ASAP) = 981.2.

Example 3

15-(3-(4-([1,1':3',1"-tetraphenyl]-5'-yl)-6-phenyl-1,3,5-triazinyl-2-yl Phenyl)-5,10-diphenyl-10,15-dihydro-5H-pyrrole[3,2-c:4,5-c']dioxazole

4.98 g of a 250 ml three-necked flask, 10 mmol of 5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c']dicarbazole, 5.94 g, 11.0 mmol 2 -([1,1':3',1"-tetraphenyl]-5'-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 6.9 g, 50 mmol potassium carbonate, 0.26 g, 1 mmol 18-crown-6, 3.0 g, 15 mmol of cuprous iodide and 150 ml of o-dichlorobenzene, reacted at 160 ° C in a N ₂ atmosphere, and the reaction progressed by TLC until the reaction was completed. cooled to room temperature. the reaction solution was poured into water, washed to remove K ₂ CO _3, then suction filtered to give the solid product was washed with methylene chloride. toluene / petroleum ether mixed solvent and recrystallized to give the product as a white solid powder 15 ( 3-(4-([1,1':3',1"-tetraphenyl]-5'-yl)-6-phenyl-1,3,5-triazinyl-2-yl)phenyl -5,10-Diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c'] oxazole 7.8 g. MS (ASAP) = 958.1.

Example 4

4,4'-bis(5,10-diphenyl-5,10-dihydro-15H-pyrrole[3,2-c:4,5-c']dioxazole-15-yl)-1 , 1'-diphenyl

4.98 g of a 250 ml three-necked flask, 10 mmol of 5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c']dicarbazole, 1.56 g, 5 mmol 4 , 4'-dibromo-1,1'-diphenyl, 2.4 g, 25 mmol sodium t-butoxide, 0.44 g, ₂ mmol Pd(OAc) ₂ , 150 ml toluene, reacted in a N ₂ atmosphere at 110 ° C, TLC tracking reaction The process, until the reaction is over, is reduced to room temperature. The reaction solution was poured into water, washed with sodium t-butoxide, and suction filtered to give a solid product which was dissolved in dichloromethane to remove impurities. Recrystallization from dioxane to give the product solid powder 4,4'-bis(5,10-diphenyl-5,10-dihydro-15H-pyrrole[3,2-c:4,5-c' And dicarbazole-15-yl)-1,1'-diphenyl 4.0g. MS (ASAP) = 1145.3.

Example 5

15-(4-(dibenzo[b,d]furan-4-yl)phenyl)-5,10-diphenyl-10,15-dihydro-5H-pyrrolo[3,2-c: 4,5-c']dicarbazole

4.98 g of a 250 ml three-necked flask, 10.0 mmol of 5,10-diphenyl-10,15-dihydro-5H-pyrrole [3,2-c:4,5-c']dicarbazole, 3.54 g, 11.0 Ment 4-(4-bromophenyl)dibenzo[b,d]furan, 2.4 g, 25 mmol sodium t-butoxide, 0.44 g, ₂ mmol Pd(OAc) ₂ , 150 ml toluene, reacted in a N ₂ atmosphere at 110 ° C The TLC tracks the progress of the reaction and waits for the reaction to end and falls to room temperature. The reaction solution was poured into water, and the sodium tert-butoxide was removed by washing, followed by suction filtration to obtain a solid product which was dissolved in chloroform to remove impurities. Recrystallization from dioxane and ethanol gave the product solid powder 4,4'-bis(5,10-diphenyl-5,10-dihydro-15H-pyrrolo[3,2-c:4,5 -c'] Dicarbazole-15-yl)-1,1'-diphenyl 6.0g. MS (ASAP) = 740.4.

The energy level of the organic compound material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S ₁ , T ₁ and the resonance factor f(S ₁ ) are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them HOMO (G) and LUMO (G) are direct calculation results of Gaussian 09W, the unit is Hartree. The results are shown in Table 1:

Table I

材料material	HOMO[eV]HOMO[eV]	LUMO[eV]LUMO[eV]	T₁[eV]T ₁ [eV]	S₁[eV]S ₁ [eV]	ΔE_ST ΔE _ST
(1)(1)	-5.22-5.22	-2.91-2.91	2.312.31	2.352.35	0.030.03
(2)(2)	-5.16-5.16	-2.46-2.46	2.732.73	2.852.85	0.120.12
(3)(3)	-5.13-5.13	-2.92-2.92	2.322.32	2.322.32	0.010.01
(4)(4)	-5.18-5.18	-2.62-2.62	2.742.74	2.752.75	0.010.01
(5)(5)	-5.11-5.11	-2.54-2.54	2.752.75	2.822.82	0.060.06

Ref1

-5.08

-3.14

1.90

1.91

0.01

Wherein, the value of ΔE(S ₁ -T ₁ ) is not more than 0.12 eV, and the delayed fluorescent luminescence condition of less than 0.30 eV is satisfied.

In contrast to the extended fluorescent luminescent material described above, the delayed fluorescent luminescent material of the D-A architecture is labeled with Ref 1 :

Preparation of OLED devices:

The preparation steps of an OLED device having ITO/NPD (35 nm) / 5% (1) - (5): mCP (15 nm) / TPBi (65 nm) / LiF (1 nm) / Al (150 nm) / cathode are as follows:

a, cleaning of the conductive glass substrate: when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;

b, HTL (35 nm), EML (15 nm), ETL (65 nm): thermally evaporated in a high vacuum (1 × 10 ^-6 mbar, mbar);

c, cathode: LiF / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. After detection, the luminous efficiency and lifetime of OLED1 (corresponding to the host material (1)) are more than three times that of OLED Ref1 (corresponding to the host material (Ref1)), and the luminous efficiency of OLED3 (corresponding to the host material (3)) is OLED Ref1. 4 times, and the lifetime is more than 6 times, especially the maximum external quantum efficiency of OLED 3 is more than 12%. It can be seen that the OLED device prepared by using the organic mixture of the invention has greatly improved luminous efficiency and lifetime, and the external quantum efficiency is also significantly improved.

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

An organic compound having the structural features shown in formula (1):

among them,

Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 or Ar 7 are the same or different and are selected from aromatic, heteroaromatic or non-aromatic ring systems having 2 to 40 carbon atoms, and are One or more R 1 substituted or unsubstituted;

R 1 is optionally selected from the group consisting of: H; D; a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group; a branched or cyclic alkyl group having 3 to 20 C atoms; Alkoxy, thioalkoxy or silyl; substituted keto group having 1 to 20 C atoms; alkoxycarbonyl group having 2 to 20 C atoms; having 2 to 10 carbon atoms Aryl or heteroaryl; aryloxycarbonyl having 7 to 20 C atoms; cyano; carbamoyl; haloformyl; formyl; isocyano; isocyanate; thiocyanate; isothiocyanate Acid ester group; hydroxyl group; nitro group; CF 3 ; Cl; Br; F; crosslinkable group; substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; ～40 aryloxy or heteroaryloxy groups of a ring-forming atom;

n is 1 or 2;

n 1 is 0 or 1;

X, Y, Q, Z, U are single bonds or bridged groups which are bonded to Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 or Ar 6 by a single bond or a double bond; wherein X, Y, At least one of Q is different from Z or U.
The organic compound according to claim 1, wherein X, Y, Q, Z, U are the same or different and are selected from a single bond, a two bridged group or a triple bridged group;

The second bridging group is selected from:

Wherein R 3 , R 4 and R 5 have the same meaning as R 1 ;

The three bridging groups are selected from:

Wherein R 4 , R 5 and R 6 have the same meanings as R 1 .
The organic compound according to claim 2, wherein X, Y and Q are each a single bond, and Z and U are both
The organic compound according to claim 1, wherein Ar 1 , Ar 2 , Ar 3 , and Ar 4 are the same or different and are selected from the group consisting of:

Wherein X 1 is selected from CR 6 or N;

Y 1 is selected from CR 7 R 8 , SiR 9 R 10 , NR 11 or C(=O), S, or O;

R 6 , R 7 , R 8 , R 9 , R 10 and R 11 have the same meanings as R 1 .
The organic compound according to claim 4, wherein Ar 1 , Ar 2 , Ar 3 , and Ar 4 are the same or different and are selected from:
The organic compound according to claim 1, wherein Ar 5 , Ar 6 and Ar 7 are the same or different and are selected from the group consisting of:

n 2 is 1 or 2 or 3 or 4.
The organic compound according to claim 6, wherein Ar 5 , Ar 6 and Ar 7 are the same or different, optionally:
The organic compound according to claim 1, wherein at least one of Ar 5 , Ar 6 , and Ar 7 includes an electron-donating group, and/or at least one includes an electron-withdrawing group.
The organic compound according to claim 8, wherein the electron-donating group is selected from the group consisting of substituted or unsubstituted:
The organic compound according to claim 8, wherein the electron withdrawing group is selected from the group consisting of F, a cyano group or the following groups:

Where n 3 is 1, 2, 3 or 4;

X 2 -X 9 are optionally selected from CR or N, and at least one is N;

Z 1 , Z 2 , and Z 3 are each selected from N(R), C(R) 2 , Si(R) 2 , O, C=N(R), C=C(R) 2 , P(R). , P (= O) R, S, S = O, SO 2 or absent, but at least not without a;

R is optionally selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
The organic compound according to claim 1, which has the structural features of the formulae (2) to (5):
The organic compound according to claim 11, which has the structural features of the formulae (6) to (21):
The organic compound according to claim 12, which has the structural features as shown in the formula (6):
The organic compound according to any one of claims 1 to 13, which is selected from the group consisting of:
A high molecular polymer characterized by comprising the structural features of the organic compound according to any one of claims 1 to 14 in a repeating unit.
An organic photoelectric material, comprising the organic compound according to any one of claims 1 to 14 or the high molecular polymer according to claim 15, and at least one organic functional material; Self-hole note Into materials, hole transport materials, electron transport materials, electron injecting materials, electron blocking materials, hole blocking materials, illuminants, host materials and organic dyes.
An organic photoelectric composition comprising the organic compound according to any one of claims 1 to 14 or the high molecular polymer according to claim 15, and at least one organic solvent.
Use of the organic compound according to any one of claims 1 to 14 or the polymer according to claim 15 in an organic electronic device.
An organic electronic device comprising the organic compound according to any one of claims 1 to 14 and/or the high molecular polymer according to claim 15.
The organic electronic device according to claim 19, wherein the organic electronic device is an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic spintronic device. Device, organic sensor or organic plasmon emitting diode.
The organic electronic device according to claim 19, wherein the organic electronic device comprises a light emitting layer;

The light-emitting layer includes the organic compound according to any one of claims 1 to 14 or the high molecular polymer according to claim 15.
The organic electronic device according to claim 21, wherein the light emitting layer further comprises a phosphorescent emitter and/or a host material.