WO2018095387A1 - Organic chemical compound and application thereof, organic mixture, and organic electronic component - Google Patents

Abstract

Provided are an organic chemical compound and application thereof, organic mixture, and organic electronic component; the structure of said organic chemical compound is as shown in general formula (1); the definition of the substituent group in the general formula (1) is the same as in the description.

Description

Organic compounds and their applications, organic mixtures, organic electronic devices

The present application claims priority to Chinese Patent Application No. 20161104691, filed on Nov. 23, 2016, the entire disclosure of which is incorporated herein by reference. In this application.

Technical field

The invention relates to the technical field of organic photoelectric materials, in particular to an organic compound and an application thereof, an organic mixture and an organic electronic device.

Background technique

Organic semiconductor materials are versatile in synthesis, relatively low in manufacturing cost, and excellent in optical and electrical properties. In particular, Organic Light-Emitting Diodes (OLEDs) have great potential in the application of optoelectronic devices such as flat panel displays and illumination.

In order to improve the luminous efficiency of organic light emitting diodes, various fluorescent and phosphorescent based luminescent material systems have been developed. Organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescence quantum efficiency is limited to 25% under electrical excitation, because of the branching ratio of singlet excited state and triplet excited state of excitons It is 1:3. In contrast, organic light-emitting diodes 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.

In general, phosphorescent materials having 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 relatively 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 (Thermally Activated 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 difference between the singlet state (S1) and the triplet state (T1) of the organic compound (ΔEST). After a period of development, red and green TADF materials have achieved certain results in many performances. However, compared with phosphorescent materials, there is still a certain gap in performance compared with efficiency and lifetime.

Summary of the invention

In accordance with various embodiments of the present application, an organic compound and its use, organic mixture, organic electronic device are provided that address one or more of the problems involved in the background art.

An organic compound for an organic electronic device, the structure of which is as shown in the general formula (1):

among them,

Ar ^{1 is} selected from aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 carbon atoms; Ar ² is absent or Ar ^{2 is} selected from aromatic, heteroaromatic or non-carbon having 5 to 60 carbon atoms An aromatic ring system; Ar ¹ has a group R ¹ on the ring; when Ar ^{2 is} selected from an aromatic, heteroaromatic or non-aromatic ring system having 5 to 60 carbon atoms, the ring of Ar ² is Has a group R ¹ ;

X is selected from N or CR ² and adjacent X is different from N; Y ₁ and Y _{2 are} independently selected from C, Si or Ge; Z is selected from a di- or tri-bridged group, and Z is bonded to Ar ¹ or Ar ² connected by a single key or double key;

R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear alkane, alkane ether, containing 1 to 10 a carbon atom alkane sulfide, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms;

R ^{3 is} selected from the group consisting of H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, or an unsubstituted aromatic ring or an aromatic hetero group having 5 to 10 ring atoms;

R ^{2 is} selected from the group consisting of H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group of 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thio group having 3 to 20 C atoms An alkoxy group, a silyl group, a substituted keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, having 7 to 20 C atoms An aryloxycarbonyl group, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanato group, an isocyanate group, a thiocyanate group, isothiocyanate Ester group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group, substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms a ring system and one or more of an aryloxy or heteroaryloxy group having 5 to 40 ring atoms.

The use of the above organic compounds in organic electronic devices.

A polymer in which at least one repeating unit comprises the above organic compound.

An organic mixture for an organic electronic device, the organic mixture comprising at least one organic functional material and the above organic compound; the organic functional material being selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, and an electron Injecting material, electron transporting material, electron blocking material, organic host material or luminescent material.

A composition comprising an organic solvent and the above organic compound or the above polymer.

An organic electronic device comprising a functional layer, the functional layer of the above organic compound or the above polymer or the above organic mixture, or the functional layer is prepared from the above composition.

Details of one or more embodiments of the invention are set forth in the accompanying drawings and description below. Other features, objects, and advantages of the invention will be apparent from the description and appended claims.

detailed description

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In this context, compositions, printing inks, and inks have the same meaning and are interchangeable. The host material, matrix material, Host material, and Matrix material have the same meaning and are interchangeable. Metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

The structure of the organic compound for an organic electronic device of an embodiment is as shown in the general formula (1):

among them,

Ar ^{1 is} selected from aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 carbon atoms; Ar ² is absent or Ar ^{2 is} selected from aromatic, heteroaromatic or non-carbon having 5 to 60 carbon atoms An aromatic ring system; Ar ¹ has a group R ¹ on the ring; when Ar ^{2 is} selected from an aromatic, heteroaromatic or non-aromatic ring system having 5 to 60 carbon atoms, the ring of Ar ² is Has a group R ¹ ;

X is selected from N or CR ² and adjacent X is different from N; Y ₁ and Y _{2 are} independently selected from C, Si or Ge; Z is selected from a di- or tri-bridged group, and Z is bonded to Ar ¹ or Ar ² connected by a single key or double key;

R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear alkane, alkane ether, containing 1 to 10 a carbon atom alkane sulfide, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms;

R ^{3 is} selected from the group consisting of H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, or an unsubstituted aromatic ring or an aromatic hetero group having 5 to 10 ring atoms;

R ^{2 is} selected from the group consisting of H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group of 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thio group having 3 to 20 C atoms An alkoxy group, a silyl group, a substituted keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, having 7 to 20 C atoms An aryloxycarbonyl group, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group (-C(=O)-X, wherein X represents Halogen atom), formyl group (-C(=O)-H), isocyanate group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group a group, a CF ₃ group, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, and having 5 to 40 ring atoms one or more aryloxy or heteroaryloxy group of; R ² form a monocyclic group bonded to the ring Polycyclic aliphatic or aromatic ring plurality of R ² form a monocyclic or polycyclic, aliphatic or aromatic ring with each other.

Incidentally, substitutable ring positions on Ar ² may be unsubstituted or substituted with R ^1, when R ¹ is present in a plurality of times may be the same or different.

The above organic compound comprises at least two spiro ring structural units having thermal excitation delayed fluorescence luminescence (TADF) Sex. 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 can improve the luminous efficiency and lifetime of the electroluminescent device, and provides a manufacturing cost, high efficiency, long life, and low rolling. A solution for falling light-emitting devices.

In one embodiment, Ar ¹ -Ar ^{2 are} independently selected from an aromatic or heteroaromatic hydrocarbon system that is unsubstituted or substituted with R ¹ .

In one embodiment, Ar ¹ -Ar ^{2 are} independently selected from aromatic or heteroaromatic rings having from 2 to 20 carbon atoms which are unsubstituted or substituted with R ¹ .

In one embodiment, Z is selected from a second bridge or a triple bridge.

In one embodiment, Z is selected from a triple bridging group comprising any of the following structural formulae.

Wherein R ₄ , R ₅ and R _{6 are} independently selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear An alkane, an alkane ether, an alkane thioether having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms; a dotted line indicating any of said triple bridging groups and structural unit Ar ¹ , Ar ² or a C-bonded bond on the benzene ring.

In one embodiment, Z is selected from the group consisting of the triple bridging groups shown in any of the above formulas.

In one embodiment, Ar ² is absent and Z is selected from a di bridging group comprising any of the following structural formulae.

Wherein R ₄ and R _{5 are} independently selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear alkanes, alkanes An ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms; a dotted bond indicating any of the above-mentioned two bridging groups and a structural unit Ar ¹ or benzene C-bonded bond on the ring.

In one embodiment, at least one of Y ₁ and Y ₂ is C. In one embodiment, Y ₁ and Y ₂ are each selected from C;

In one embodiment, Ar ^{1 is} selected from an aromatic, heteroaromatic or non-aromatic ring system having from 5 to 20 carbon atoms.

In one embodiment, Ar ^{1 is} selected from aromatic or heteroaromatic having 5-20 carbon atoms. Further, in one embodiment, Ar ^{1 is} selected from an aromatic or heteroaromatic having 5 to 18 carbon atoms. Ar ^{1 is} selected from aromatic or heteroaromatic groups having 5 to 16 carbon atoms. Ar ^{1 is} selected from aromatic or heteroaromatic groups having 5 to 13 carbon atoms.

In one embodiment, Ar ^{2 is} selected from aromatic or heteroaromatic having from 5 to 60 carbon atoms. In one embodiment, Ar ^{2 is} selected from aromatic or heteroaromatic having 5 to 50 carbon atoms. In one embodiment, Ar ^{2 is} selected from aromatic or heteroaromatic having from 5 to 40 carbon atoms. In one embodiment, Ar ^{2 is} selected from aromatic or heteroaromatic having 5 to 25 carbon atoms.

For the purposes of the present invention, an aromatic ring system contains more than 6 ring atoms in the ring system. The heteroaromatic ring system contains more than 5 ring atoms and at least one hetero atom in the ring system, provided that the total number of carbon atoms and heteroatoms is at least 4. The hetero atom is selected from one or more of Si, N, P, O, S, and Ge. In one embodiment, the hetero atom is selected from one or more of Si, N, P, O, and S. It should be noted that the aromatic or heteroaromatic ring system includes not only an aromatic or heteroaromatic system, but also a plurality of aryl or heteroaryl groups may be interrupted by short non-aromatic units (<10%). Non-H atoms, such as C, N or O atoms). In one embodiment, a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (less than 10% atomic percentage of non-H 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.

For the purposes of the present invention, non-aromatic ring systems contain from 1 to 10 carbon atoms in the ring system and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or mono- or by the group R ¹ Multiple substitutions, the groups R ¹ may be the same or different in each occurrence. In one embodiment, the non-aromatic ring system contains from 1 to 3 carbon atoms in the ring system. In one embodiment, the non-aromatic ring system may also contain one or more heteroatoms. Wherein, the hetero atom may be selected from one or more of Si, N, P, O, S, and Ge. In one embodiment, the hetero atom is selected from one or more of Si, N, P, O, and 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.

For the purposes of the present invention, a H atom or a bridging CH ₂ group on NH may be substituted with an R ¹ group. In one embodiment, R ^{1 is} selected from the group consisting of: (1) a C1-C10 alkyl group, wherein the C1-C10 alkyl group may refer to the group: methyl, ethyl, n-propyl, isopropyl, cyclo Propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl Base, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentene Base, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octyne (2) a C1-C10 alkoxy group, wherein the C1-C10 alkoxy group may be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, or a secondary group. Butoxy, tert-butoxy or 2-methylbutoxy; (3) C2 to C10 aryl or heteroaryl, which may be monovalent or divalent depending on the use, and in each case also Substituted by the above mentioned group R1 and can be passed through any desired position with aromatic or heteroaryl Aroma ring connection. In one embodiment, the C2 to C10 aryl or heteroaryl group is selected from the group consisting of benzene, naphthalene, anthracene, perylene, dihydroanthracene, fluorene, fluorene, fluoranthene, butyl, pentane, benzene. And hydrazine, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole , oxazole, imidazole, benzimidazole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphtazole, oxazole , 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-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, hydrazine or 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 ¹ and Ar ^{2 are} independently selected from aromatic, heteroaromatic or non-aromatic ring systems having 5 or more carbon atoms, which may be unsubstituted or substituted by one or two R ¹ groups. Replace. In one embodiment, the aromatic or heteroaromatic ring is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyridine, perylene or thiophene.

In one embodiment, Ar ¹ or Ar ² , particularly Ar ^{1 ,} comprises any of the following structural formulas. Any of the following structural formulas may be substituted by one or more groups R ¹ .

Wherein X _{1 is} selected from CR ⁷ or N; Y is selected from CR ⁸ R ⁹ , SiR ¹⁰ R ¹¹ , NR ¹² , C(=O), S or O;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{12 are} independently selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a branched or cyclic silyl group having 3 to 20 C atoms, having 1 to 20 C atoms Substituted keto group, alkoxycarbonyl group having 2 to 20 C atoms, aryloxycarbonyl group having 7 to 20 C atoms, cyano group, carbamoyl group, halogen Formyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl , Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, an aryloxy group or a heteroaryloxy group having 5 to 40 ring atoms one or more ^{radicals; R 7, R 8, R} 9, R 10 R ^11, R ¹² bonded to at least one of the structural groups of the key ring form a monocyclic or polycyclic, aliphatic or aromatic ring, or ^{R 7, R 8, R 9} , R 10, R 11, R 12 At least two of the two are bonded to each other to form a monocyclic or polycyclic aliphatic or aromatic ring.

It should be noted that Ar ^{1 is} selected from any of the following groups.

In one embodiment, Ar ¹ or Ar ² , particularly Ar ^{1 ,} comprises the following structural formula. Any of the following structural formulas may be further substituted with one or more groups R ₁ .

In one embodiment, both Y ₁ and Y ₂ are selected from C and Ar ¹ is phenyl.

In one embodiment, Ar ² comprises the following structural units or a combination thereof.

Where n is 1, 2, 3 or 4.

Further, in one embodiment, Ar ^{2 is} selected from any of the groups listed above.

In one embodiment, the organic compound has a higher triplet energy level T ₁ , T ₁ 2.0 eV. In one of the embodiments, T ₁ ≥ 2.2 eV. Further, in an embodiment, T ₁ ≥ 2.4 eV. In one of the embodiments, T ₁ ≥ 2.6 eV. In one of the embodiments, T1 ≥ 2.8 eV.

Generally, the triplet level T1 of an organic compound depends on the substructure of the compound having the largest conjugated system. Generally, T1 decreases as the conjugated system increases. In one of the embodiments, the molecular structure represented by the following formula (1a) in the chemical formula (1) has the largest conjugated system.

In one embodiment, the formula (1a) has no more than 30 carbon atoms in the case of removing a substituent. In one embodiment, the formula (1a) has no more than 26 carbon atoms in the case of removing a substituent. In one embodiment, the formula (1a) has no more than 22 carbon atoms in the case of removing a substituent. In one embodiment, the formula (1a) has no more than 20 carbon atoms in the case of removing a substituent.

In one of the embodiments, the general formula (1a) has a higher triplet energy level T ₁ , T ₁ 2.0 eV. In one of the embodiments, T ₁ 2.2 eV. In one of the embodiments, T _{1 is} 2.4 eV. In one of the embodiments, T _{1 is} 2.6 eV. In one of the embodiments, T ₁ 2.8 eV.

The compounds according to the invention facilitate the obtaining of thermally excited delayed fluorescent TADF properties. According to the principle of thermal excitation delayed fluorescent TADF material (see Adachi et al., Nature Vol 492, 234, (2012)), when the ΔE(S ₁ -T ₁ ) of the organic compound is sufficiently small, the triplet excitons of the organic compound can pass Reverse internal conversion to singlet excitons for efficient illumination. Wherein ΔE(S ₁ -T ₁ ) represents an energy level difference between the first triplet excited state T _{1 of} the organic compound and the first singlet excited state S ₁ . In general, TADF materials are obtained by electron donating (Donor) to electron-deficient or acceptor groups, i.e., having a distinct DA structure.

In one embodiment, the organic compound has ΔE(S ₁ -T ₁ ) ≤0.30 eV. In one embodiment, the organic compound has ΔE(S ₁ -T ₁ ) ≤ 0.25 eV. In one embodiment, the organic compound has ΔE(S ₁ -T ₁ )≤0.20 eV. In one embodiment, the organic compound has ΔE(S ₁ -T ₁ )≤0.10 eV.

In one embodiment, the organic compound according to formula (1), wherein Ar ² comprises an electron donating group or comprises an electron withdrawing group.

In one embodiment, the electron donating group comprises the following groups.

In one embodiment, the electron donating group is selected from any of the groups listed above.

In one embodiment, the electron withdrawing group is selected from the group consisting of F, cyano, or a structural formula containing any of the following groups.

Wherein n is 1, 2 or 3; X1 - X8 are independently selected from CR ¹³ or N, and at least one of X ¹ - X ⁸ is N; R ^{13 is} selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene , alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

Further, in one of the embodiments, the electron withdrawing group is selected from any of the above groups.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤ 4000 g/mol. Further, the molecular weight of the small molecule is ≤3000 g/mol. Further, the molecular weight of the small molecule is ≤2000 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.].

The conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp ² hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene). 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, by the substituents on the unit of the formula (1) and optionally on the benzene ring unit present, the two spiro ring structures give the molecule a large rigid structure, ensuring the solubility of the organic small molecule compound. If Ar ² has other substituents such as an alkane group, these substituents can also promote solubility.

The structural unit of the formula (1) is suitable for various functions in an organic small molecule compound 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, it is described by the group Ar ² which compounds are particularly suitable for which functions. Ar ² has an influence on the electronic properties of the unit of the formula (1).

In one embodiment, H on the organic compound is at least partially deuterated. In one of the embodiments, 10% of the H is deuterated. In one of the embodiments, 20% of the H is deuterated. In one of the embodiments, 30% of the H is deuterated. In one of the embodiments, 40% of the H is deuterated.

In one embodiment, the organic compound represented by the formula (1) is one selected from the group consisting of compounds represented by any of the following structural formulas. These structures can be substituted at all possible points of substitution.

The use of the above organic compounds in a mixture.

The use of the above organic compounds in the compositions.

The use of the above organic compounds in organic electronic devices.

The polymer of one embodiment, wherein at least one repeating unit comprises an organic compound as shown in the formula (1). In one of the embodiments, the polymer is a non-conjugated polymer in which the structural unit represented by the formula (1) is on the side chain. In other embodiments, the polymer is a conjugated polymer.

The use of the above polymers in the compositions. The above polymers can be used in mixtures. The above polymers can also be used in organic electronic devices.

The organic mixture of an embodiment comprises the above organic compound, and at least one other organic functional material. The organic functional material is selected from the group consisting of a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), and an electron blocking material (EBM). , organic host material (Host), singlet emitter (fluorescent emitter), heavy emitter (phosphorescent emitter) or organic thermal excitation delayed fluorescent material (TADF material). The organic thermal excitation delayed fluorescent material may be a light emitting organic metal complex. Various organic functional materials are described in detail in, for example, WO 2010135519 A1, US 2009 0 134 784 A1, and WO 2011110277 A1, the entire contents of each of which is hereby incorporated by reference. The organic functional material may be a small molecule or a high polymer material.

In one embodiment, the organic mixture comprises the above organic compound and a phosphorescent emitter. Here, the organic compound according to the present invention can be used as a host, and in this case, the phosphorescent light body weight percentage is ≤ 30% by weight. In one implementation, the phosphorescent emitter weight percentage is <25 wt%. In one implementation, the phosphorescent emitter weight percentage is < 20 wt%.

In one embodiment, the organic mixture comprises the above organic compound and a host material. Here, the organic compound according to the present invention can be used as a light-emitting material, in which case the weight percentage of the organic compound is ≤ 30% by weight. In one embodiment, the weight percent of organic compound is <25 wt%. In one embodiment, the weight percent of organic compound is < 20 wt%. In one embodiment, the weight percent of organic compound is < 15 wt%.

In one embodiment, the organic mixture comprises the above organic compound, a phosphorescent emitter, and a host material. In one embodiment, the organic compound according to the invention may be used as an auxiliary luminescent material in a weight ratio to phosphorescent emitter of from 1:2 to 2:1. In another embodiment, the organic compound according to the present invention is higher than the T ₁ of T ₁ of the phosphorescent material.

In one embodiment, the organic mixture comprises the above organic compound and another TADF material.

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

1. Triplet Host Material (Triplet Host):

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 two-dentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P or S; L is an ancillary ligand; m is an integer, The value is from 1 to the maximum coordination number of this metal; m+n is the maximum coordination number of this metal.

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

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

In one embodiment, M is selected from the group consisting of Ir or 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, fluorene; or a compound containing an aromatic heterocyclic group such as dibenzothiophene. , dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, Triazoles, oxazoles, thiazoles, oxadiazoles, triazoles, dioxazoles, thiadiazoles, pyridines, pyridazines, pyrimidines, pyrazines, triazines, oxazines, oxazines, dioxazins, Anthracene, benzimidazole, carbazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene , anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopyridine, benzothienopyridine, thienopyridine, benzoselenopyridine and selenophene And dipyridine; or a group containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic Ring group, and at least one of the following groups coupled together directly or through another, 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. Wherein each Ar may be further substituted, and the substituent is selected from hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

In one embodiment, the triplet host material is selected from the group consisting of at least one of the following groups:

Wherein R ¹ -R ^{7 are} independently selected from hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl, when they are aryl or heteroaryl When they are the same as Ar ¹ and Ar ² described above; n is selected from 0, ¹ , ^2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, ¹³ , 14, 15, ¹⁶ , 17, 18, 19 or 20; X ¹ -X ^{8 is} selected from CH or N, and X ^{9 is} selected from CR ¹ R ² or NR ¹ .

Examples of suitable triplet host materials are listed in the table 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; each occurrence of L may be the same or different, and is an organic ligand which is bonded to the metal atom M by one or more position bonding or coordination; n is an integer greater than one. Preferably, it is 1, 2, 3, 4, 5 or 6. In one embodiment, the metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In one of the embodiments, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide. In one embodiment, M is selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu, or Ag. In one embodiment, M is selected from the group consisting of Os, Ir, Ru, Rh, Re, Pd, or Pt.

In one embodiment, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites. In one embodiment, the triplet emitter comprises two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand are 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-phenylquinoline. A morphine derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may 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 the group consisting of transition metal elements, lanthanides or actinides.

Ar ¹ is a cyclic group which may be the same or different at each occurrence, and Ar ¹ contains 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 and a metal Coordination linkage; Ar ² is a cyclic group, which may be the same or different at each occurrence, Ar ² contains at least one C atom through which a cyclic group is bonded to the metal; Ar ¹ and Ar ² are covalently The linkages are linked together and may each carry one or more substituent groups, which may also be joined together by a substituent group; L may be the same or different at each occurrence, and L is an auxiliary ligand, preferably a double-sided chelate The ligand, preferably a monoanionic bidentate chelate ligand; m is selected from 1, 2 or 3; n is selected from 0, 1 or 2. In one embodiment, L is a bidentate chelate ligand. In one embodiment, L is a monoanionic bidentate chelate ligand. In one of the embodiments, m is 2 or 3. In one of the embodiments, m is 3. In one of the embodiments, n is 0 or 1. In one of the embodiments, n is zero.

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, WO 2010099852, 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 6824895, US 7029766, US 6835469, US 6830828, US 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%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their 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.

TADF materials need to have a small singlet-triplet energy level difference. In one of the embodiments, ΔEst < 0.3 eV. In one of the embodiments, ΔEst < 0.2 eV. In one of the embodiments, ΔEst < 0.1 eV. In one of the embodiments, the TADF material has a relatively small ΔEst. In another embodiment, TADF has 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.

In one embodiment, the above organic compound is used to print an OLED having a molecular weight of ≥ 700 g/mol. In one embodiment, the molecular weight of the organic compound is > 800 g/mol. In one embodiment, the molecular weight of the organic compound is > 900 g/mol. In one embodiment, the molecular weight of the organic compound is > 1000 g/mol. In one embodiment, the molecular weight of the organic compound is > 1100 g/mol.

In one embodiment, the above organic compound or organic mixture has a solubility in toluene of > 10 mg/ml at 25 °C. In one of the examples, the solubility in toluene is > 15 mg/ml. In one of the examples, the solubility in toluene is > 20 mg/ml.

The use of the above organic mixture in organic electronic devices.

The organic mixture of another embodiment includes the above-mentioned polymer, and the various components and contents of the organic mixture are the same as those of the organic mixture of the above embodiment, and will not be described herein.

The composition of an embodiment comprises an organic solvent and the above organic compound or polymer. In this embodiment, the composition is an ink. Thus, the viscosity and surface tension of the ink are important parameters when the composition is used in a printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.

In one embodiment, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 19 dyne/cm to 50 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 22 dyne/cm to 35 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 25 dyne/cm to 33 dyne/cm.

In one embodiment, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1 cps to 100 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or 25 ° C is in the range of 1 cps to 50 cps, in one of the examples, the viscosity of the ink at the operating temperature or 25 ° C. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1.5 cps to 20 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 4.0 cps to 20 cps. This makes the composition more convenient for 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. An ink containing a metal organic complex or a polymer facilitates the adjustment of the printing ink to an appropriate range in accordance with the printing method used. The weight ratio of the organic functional material contained in the composition is from 0.3% to 30% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 20% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 15% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 10% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 1% to 5% by weight.

In an embodiment, the organic solvent comprises a first solvent selected from the group consisting of aromatic and/or heteroaromatic based solvents. Further, the first solvent may be an aliphatic chain/ring-substituted aromatic solvent, or an aromatic ketone solvent, or an aromatic Ether solvent.

Examples of the first solvent are, but not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene. , 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, trimerene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, 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-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, two Benzene, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl) Pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy a 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-indolone, anthrone, 2-nonanone, 3- Anthrone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzyl Butylbenzene, 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 Ether, dioctyl ether, ethylene glycol 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; ester solvent: octanoic acid Alkyl esters, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamate, alkyl oxalates, alkyl maleates, alkanolactones, alkyl oleates, and the like.

Further, the first solvent may also be selected from aliphatic ketones, for example, 2-nonanone, 3-fluorenone, 5-fluorenone, 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 glycol dibutyl ether, diethylene glycol II 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 and tetraethylene One or more of the glycerols.

In one embodiment, the organic solvent further includes a second solvent selected from the group consisting of 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-benzene Oxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl One or more of a sulfoxide, tetrahydronaphthalene, decalin, and anthracene.

In an embodiment, the composition can be a solution or suspension. This is determined based on the compatibility between the organic mixture and the organic solvent.

In one embodiment, the weight percentage of organic compound in the composition is from 0.01 to 20% by weight. In one embodiment, the weight percentage of organic compound in the composition is from 0.1 to 15% by weight. In one embodiment, the weight percentage of organic compound in the composition is from 0.2 to 10% by weight. In one embodiment, the weight percent of organic compound in the composition is from 0.25 to 5 wt%.

In one embodiment, the above composition is used in the preparation of an organic electronic device. In particular, its use as a coating or printing ink in the preparation of an organic electronic device is particularly preferred by a printing or coating preparation method.

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 or slit-type extrusion coating. Preferred are gravure, inkjet and inkjet printing. The composition may further include a component example, and the cap component is selected from one or more of a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder, thereby being used for adjusting viscosity. , film formation performance, improve attachment Sexuality and so on. 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.

In one embodiment, the use of the above organic compound or polymer in an organic electronic device is such that the organic compound or polymer is applied to an organic electronic device. The organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device. Luminescent field effect transistor, organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode. In an embodiment, the organic electronic device is an electroluminescent device such as an OLED, an OLEEC, and an organic light-emitting field effect transistor. Further, the organic compound is used for the light-emitting layer of the electroluminescent device.

The organic electronic device of an embodiment comprises at least one of the above-described organic compounds or organic mixtures. Wherein, the organic electronic device may include a cathode, an anode, and a functional layer between the cathode and the anode, the functional layer comprising the above organic compound or the above polymer or the above organic mixture, or the functional layer is prepared from the above composition. Specifically, the organic electronic device comprises at least a cathode, an anode and a functional layer between the cathode and the anode, the functional layer comprising at least one of the above organic compounds or the above polymer or the above organic mixture, or the functional layer is prepared from the above composition Made. The functional layer is selected from one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a light emitting layer.

The organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device. Luminescent field effect transistor, organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode. In one embodiment, the organic electronic device is an organic electroluminescent device such as an OLED, OLEEC or organic light-emitting field effect transistor. Further, the organic light emitting diode may be an evaporation type organic light emitting diode or a printed organic light emitting diode.

In one embodiment, the light emitting layer of the organic electroluminescent device comprises one of the above organic compounds or polymers, or comprises one of the above organic compounds or polymers and a phosphorescent emitter, or comprises one of the above organic compounds Or a high polymer and a host material, or comprise one of the above organic compounds or polymers, a phosphorescent emitter, and a host material.

In an embodiment, the organic electroluminescent device comprises a substrate, an anode, a light-emitting layer, and a cathode, which are sequentially stacked. Wherein, the number of layers of the light-emitting layer is at least one layer.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent luminescent component, see 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 also be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In one embodiment, the substrate is flexible, optionally in a polymeric film or plastic, having a glass transition temperature Tg of 150 ° C or higher. The flexible substrate can be poly(ethylene terephthalate) (PET) or polyethylene glycol (2,6-naphthalene) (PEN). In one of the embodiments, the substrate has a glass transition temperature Tg of 200 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 250 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 300 ° C or higher.

The anode can include 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 0.5eV. 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 0.3 eV. 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 0.2 eV. Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum doped zinc oxide (AZO). Wait. The anode material can also be other materials. 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 other embodiments, the anode is patterned. A patterned ITO conductive substrate is commercially available and can be used to prepare an organic electronic device according to the present embodiment.

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 or conductance of the illuminant in the luminescent layer or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference in band level is less than 0.5 eV. The work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer The absolute value is less than 0.3 eV. The work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer The absolute value is less than 0.2 eV. All materials which can be used as the cathode of the OLED are possible as the cathode material of the organic electronic device of the present embodiment. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/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, and electron beam (e-beam).

The OLED may further comprise 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) or 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 disclosure of which is hereby incorporated by reference.

In one of the embodiments, the light-emitting layer of the organic electroluminescent device is prepared by the above composition.

In an embodiment, the organic electroluminescent device light-emitting device has an emission wavelength between 300 and 1000 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength between 350 and 900 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength of between 400 and 800 nm.

In one embodiment, the above-described organic electronic device is used in an electronic device. The electronic device is selected from a display device, a lighting device, a light source or a sensor. Among them, the organic electronic device may be an organic electroluminescent device.

An electronic device comprising the above organic electronic device.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Example 1

5'-([1,1':3',1"-m-triphenyl]-5'-yl)-5'H-dispiro[芴-9,7'-naphtho[2,3-b ]carbazole-12',9"-芴]

5.70 g of a 250 ml three-necked flask, 10 mmol of 5'H-spirobis[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-芴], 3.41 g, 11 mmol 5 '-Bromo-1,1':3',1"-m-triphenyl, 2.76 g, 20 mmol potassium carbonate, 0.22 g, 1 mmol Pd(OAc) ₂ , P(t-Bu) ₃ 1 ml and 100 ml dry toluene, In a N ₂ atmosphere, the mixture was heated to reflux overnight, and the mixture was subjected to TLC. 200 ml of methylene chloride was added, and the organic phase was washed with water, and the organic phase was combined, filtered, and the organic solvent was evaporated to give a solid product as a solid product, which was crystallized from methylene chloride and ethanol to give a white solid powder. 5'-([1,1':3',1"-m-triphenyl]-5'-yl)-5'H-dispiro[芴-9,7'-naphtho[2,3-b ]carbazole-12',9"-芴]. MS (ASAP) = 797.4.

Example 2

5'-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5'H-spiro[[芴-9,7'-naphtho[2,3-b]咔Azole-12',9"-芴

In a 250 ml three-necked flask, 5.70 g, 10 mmol of 5'H-spirobis[芴-9,7'-naphtho[2,3-b]carbazole-12', 9"-芴], 0.5 g, 20 mmol of hydrogenated were added. Sodium, 100 ml of dry DMF, stirred at room temperature for 30 minutes, the solution turned brown, 2.97 g, 11 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine in DMF solution was added dropwise, at N ₂ atmosphere, continue to stir for 4 hours, TLC followed the progress of the reaction, until the end of the reaction, slowly quench the reaction with water. Add 200 ml of dichloromethane, washed three times with water, the organic phase is combined, dried over sodium sulfate, filtered, and evaporated to dryness The organic solvent obtained as a solid product solid product, which was recrystallized from dichloromethane and petroleum ether to give the product white solid powder 5'-(4,6-diphenyl-1,3,5-triazine-2-yl -5'H-spirobis[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-oxime. MS (ASAP) = 800.2.

Example 3

5'-(4-(9H-carbazol-9-yl)phenyl)-5'H-dispiro[芴-9,7'-naphtho[2,3-b]carbazole-12',9 "-芴"

To a 250 ml three-necked flask was added 5.70 g, 10 mmol of 5'H-spirobis[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-芴], 3.54 g, 11 mmol 9 -(4-bromophenyl)-9H-carbazole, 2.76 g, 20 mmol potassium carbonate, 0.22 g, 1 mmol Pd(OAc) ₂ , P(t-Bu) ₃ 1 ml, and 100 ml dry toluene in N ₂ atmosphere. The reaction mixture was heated to reflux overnight, and the mixture was evaporated to dryness, and then the mixture was evaporated to EtOAc. The organic product solid product is recrystallized from dichloromethane and ethanol to give the product white solid powder 5'-(4-(9H-carbazole-9-yl)phenyl)-5'H-dispiro[芴-9, 7'-naphtho[2,3-b]carbazole-12',9"-oxime]. MS (ASAP) = 810.4.

Example 4

5'-(3-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H-dispiro[芴-9,7'-naphtho[2 ,3-b]carbazole-12',9"-芴]

In this example, the final product 5'-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H-dispiro[芴-9 , 7'-naphtho[2,3-b]carbazole-12',9"-oxime] and the product of 5'-(4-(9H-carbazole-9-yl)phenyl) The synthesis procedure of -5'H-dispiro[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-芴] is the same except that the intermediate is composed of 9-( Replacement of 4-bromophenyl)-9H-carbazole with 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, reaction temperature and reaction time used in the reaction the same. The final product 5'-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H- is formed by the Hartwig reaction under the catalysis of Pd(II). Iso-[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-oxime]. MS (ASAP) = 876.5.

Example 5

5'-(2-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H-dispiro[芴-9,7'-naphtho[2 ,3-b]carbazole-12',9"-芴]

In this example, the final product 5'-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H-dispiro[芴-9 , 7'-naphtho[2,3-b]carbazole-12',9"-oxime] and the product of 5'-(3-(4,6-diphenyl-1,3, Synthesis procedure of 5-triazin-2-yl)phenyl)-5'H-dispiro[芴-9,7'-naphtho[2,3-b]carbazole-12',9′′-芴] Similarly, the difference is that the intermediate is replaced by 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine to 2-(2-bromophenyl)-4,6 -Diphenyl-1,3,5-triazine, the reaction temperature and reaction time used in the reaction process are the same. The final product 5'-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5'H- is formed by the Hartwig reaction under the catalysis of Pd(II). Bispiro[芴-9,7'-naphtho[2,3-b]carbazole-12',9"-oxime](5). MS (ASAP) = 876.4.

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, and the results are shown in Table 1.

Table I

material HOMO[eV] LUMO[eV] f(S ₁ ) T ₁ [eV] S ₁ [eV] Δ _ST (1) -5.60 -2.19 0.0054 2.94 3.04 0.10 (2) -5.87 -2.78 0.0013 2.94 3.05 0.11 (3) -5.55 -2.18 0.1192 2.94 3.05 0.11 (4) -5.61 -2.83 0.0045 2.76 2.95 0.18 (5) -5.74 -2.74 0.0032 2.94 3.14 0.20

Among them, the resonance factor f(S ₁ ) is between 0.001 and 0.119, which can improve the fluorescence quantum luminescence efficiency of the material. Further, the value of ΔE(S ₁ -T ₁ ) is not more than 0.20 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) to (5): DPEPO (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 raw material (1)) are more than twice that of OLED Ref1 (corresponding to raw material (Ref1)), and the luminous efficiency of OLED3 (corresponding to raw material (3)) is three times that of OLED Ref1. The lifetime is more than 4 times, especially the maximum external quantum efficiency of OLED 3 is more than 10%. 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.

Claims (17)

An organic compound for an organic electronic device, characterized in that the structure of the organic compound is as shown in the general formula (1):

among them, Ar ^{1 is} selected from aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 carbon atoms; Ar ² is absent or aromatic, heteroaromatic or non-aromatic of Ar ² having 5 to 60 carbon atoms Ring system; Ar ¹ has a group R ¹ on the ring; when Ar ^{2 is} selected from an aromatic, heteroaromatic or non-aromatic ring system having 5 to 60 carbon atoms, the ring of Ar ² has a group Group R ¹ ; X is selected from N or CR ² and adjacent X is different from N; Y ₁ and Y _{2 are} independently selected from C, Si or Ge; Z is selected from a di- or tri-bridged group, and Z is bonded to Ar ¹ or Ar ² connected by a single key or double key; R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear alkane, alkane ether, containing 1 to 10 a carbon atom alkane sulfide, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms; R ^{3 is} selected from the group consisting of H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, or an unsubstituted aromatic ring or an aromatic hetero group having 5 to 10 ring atoms; R ^{2 is} selected from the group consisting of H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group of 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thio group having 3 to 20 C atoms An alkoxy group, a silyl group, a substituted keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, having 7 to 20 C atoms An aryloxycarbonyl group, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanato group, an isocyanate group, a thiocyanate group, isothiocyanate Ester group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group, substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms a ring system and one or more of an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. The organic compound according to claim 1, wherein ΔE(S ₁ -T ₁ ) ≤0.30 eV of the organic compound; wherein ΔE(S ₁ -T ₁ ) represents the first three of the organic compound The energy level difference between the re-excited state T ₁ and its first singlet excited state S ₁ . The organic compound according to claim 1, wherein the Z is selected from any of the following three bridging groups:

Wherein R ₄ , R ₅ and R _{6 are} independently selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ³ ) ₂ , Si(R ³ ) ₃ , linear An alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms; a broken line bond indicating any of the triple bridging groups and the structural unit Ar ¹ , Ar ² or a C-bonded bond on the benzene ring. The organic compound according to claim 1, wherein at least one of Y ₁ and Y ₂ is C. The organic compound according to claim 1, wherein the Ar ^{1 is} selected from any of the following groups:

Wherein X _{1 is} selected from CR ⁷ or N; Y is selected from CR ⁸ R ⁹ , SiR ¹⁰ R ¹¹ , NR ¹² , C(=O), S or O; R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{12 are} independently selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a branched or cyclic silyl group having 3 to 20 C atoms, having 1 to 20 C atoms Substituted keto group, alkoxycarbonyl group having 2 to 20 C atoms, aryloxycarbonyl group having 7 to 20 C atoms, cyano group, carbamoyl group, halogen Formyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl , Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, an aryloxy group or a heteroaryloxy group having 5 to 40 ring atoms one or more ^{radicals; R 7, R 8, R} 9, R 10 R ^11, R ¹² bonded to at least one of the structural groups of the key ring form a monocyclic or polycyclic, aliphatic or aromatic ring, or ^{R 7, R 8, R 9} , R 10, R 11, R 12 At least two of the two are bonded to each other to form a monocyclic or polycyclic aliphatic or aromatic ring. The organic compound according to claim 1, wherein the Ar ^{2 is} selected from any of the following groups:

Where n is 1, 2, 3 or 4. The organic compound according to claim 1, wherein the Ar ² contains an electron donating group or an electron withdrawing group. The organic compound according to claim 7, wherein the electron-donating group is selected from any of the following groups:

The organic compound according to claim 7, wherein the electron withdrawing group is selected from the group consisting of F, cyano or any of the following groups:

Wherein n is 1, 2 or 3; X ¹ -X ^{8 are} independently selected from CR ¹³ or N, and at least one of X ¹ -X ⁸ is N; R ^{13 is} selected from hydrogen, alkyl, alkoxy, amino , alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl. The organic compound according to any one of claims 1 to 9, wherein the organic compound is one selected from the group consisting of the following structures:

Use of an organic compound according to any one of claims 1 to 10 in an organic electronic device. A polymer characterized in that at least one repeating unit of the polymer comprises the organic compound according to any one of claims 1-10. An organic mixture for an organic electronic device, characterized in that the organic mixture comprises at least one organic functional material and the organic compound according to any one of claims 1 to 10; the organic functional material is selected from the group consisting of A hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, an organic host material, or a light emitting material. A composition comprising an organic solvent and an organic compound according to any one of claims 1 to 10 or a polymer according to claim 12. An organic electronic device, characterized in that the organic electronic device comprises a functional layer comprising the organic compound according to any one of claims 1 to 10 or the polymer according to claim 12 or The organic mixture of claim 13 or the functional layer prepared from the composition of claim 14. The organic electronic device according to claim 15, wherein the organic electronic device is selected from the group consisting of 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 self. Spintronics, organic sensors or organic plasmon emitting diodes. The organic electronic device according to claim 16, wherein the organic electronic device is an organic light emitting diode, the organic electronic device comprising a light emitting layer, the light emitting layer comprising the organic compound or the polymer.