CN109790119A

CN109790119A - Organic compound and its application, organic mixture, organic electronic device

Info

Publication number: CN109790119A
Application number: CN201780059567.8A
Authority: CN
Inventors: 黄宏; 潘君友
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2016-11-23
Filing date: 2017-11-23
Publication date: 2019-05-21
Anticipated expiration: 2037-11-23
Also published as: WO2018095387A1; CN109790119B

Abstract

A kind of organic compound and its application, organic mixture, organic electronic device, shown in the structure of the organic compound such as general formula (1), the definition of the substituent group in the general formula (1) is identical as in specification.

Description

Organic compound and its application, organic mixture, organic electronic device

This application claims Patent Office of the People's Republic of China is submitted on November 23rd, 2016, application No. is 201611046914.7, the priority of the Chinese patent application of entitled " a kind of thermal excitation delayed fluorescence material and application thereof ", entire contents are hereby incorporated by reference in the application.

Technical field

The present invention relates to organic photoelectrical material technical fields, more particularly to a kind of organic compound and its application, organic mixture, organic electronic device.

Background technique

Organic semiconducting materials have diversity, the optics and electric property that manufacturing cost is relatively low and its is excellent in synthesis.Especially Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) has very big potentiality in the application aspect of photoelectric device (such as flat-panel monitor and illumination).

In order to improve the luminous efficiency of Organic Light Emitting Diode, the various luminescent material systems based on fluorescence and phosphorescence are developed.Has the characteristics that high reliablity using the Organic Light Emitting Diode of fluorescent material, but its its internal electroluminescence quantum efficiency under electrical excitation is restricted to 25%, this is because the singlet excited of exciton and the branching ratio of triplet excited state are 1:3.In contrast, almost 100% inside electroluminescence quantum efficiency is had been achieved for using the Organic Light Emitting Diode of phosphor material.But phosphorescent OLED has a significant problem, be exactly Roll-off effect, i.e. luminous efficiency are reduced rapidly with the increase of electric current or brightness, this is to high brightness using particularly disadvantageous.

Generally, the phosphor material of actual use value is iridium and platinum complex, and this raw material are rare and expensive, and the synthesis of complex is very complicated, therefore cost is also quite high.In order to overcome the raw material of iridium and platinum complex rare and expensive, and its problem that synthesis is complicated, Adachi proposes the concept of reversed internal conversion (reverse intersystem crossing), it can use organic compound in this way, metal complex is not utilized, and realizing can be the same as the high efficiency compared with phosphorescent OLED.This concept is achieved by a variety of materials combination, such as: 1) exciplex (exciplex) is utilized, referring to Adachi etc., Nature Photonics, Vol 6, p253 (2012)；2) thermal excitation delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) material is utilized, referring to Adachi et al., Nature, Vol 492,234, (2012).But the mode that the existing organic compound with TADF mostly uses greatly supplied for electronic (Donor) to be connected with electron deficient or electrophilic (Acceptor) group, it is kept completely separate so as to cause highest occupied molecular orbital (HOMO) and minimum non-occupied orbital (LUMO) Cloud Distribution, reduces the difference (△ EST) of organic compound singlet state (S1) and triplet (T1).Feux rouges and green light TADF material have in many aspect of performance through exploitation after a period of time and achieve certain achievement, but compared with phosphorescent light-emitting materials, no matter compare from efficiency or on the service life, performance still has a certain distance.

Summary of the invention

According to the various embodiments of the application, a kind of organic compound and its application, organic mixture, organic electronic device are provided, solve the problems, such as one or more involved in background technique.

A kind of organic compound for organic electronic device, shown in the structure of the organic compound such as general formula (1):

Wherein,

Ar¹Selected from aromatic series, heteroaromatic or non-aromatic ring system with 5-20 carbon atom；Ar²It is not present or Ar²Selected from aromatic series, heteroaromatic or non-aromatic ring system with 5-60 carbon atom；Ar¹Ring on all have group R¹；Work as Ar²Selected from aromatic series, heteroaromatic or when non-aromatic ring system with 5-60 carbon atom, Ar²Ring on all have group R¹；

X is selected from N or CR², and adjacent X is not all N；Y₁And Y₂Independently selected from C, Si or Ge；Z is selected from two bridges or three bridging bases, and Z and Ar¹Or Ar²It is connected with singly-bound or double bond；

R¹Selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR³)₂、Si(R³)₃, linear paraffin, alkane ether, containing 1~10 carbon atom alkane thioether, branched paraffin, cycloalkane or alkane ether group containing 3~10 carbon atoms；

R³Selected from H, D, the aliphatic alkane containing 1~10 carbon atom, aromatic hydrocarbon or containing 5~10 annular atoms take unsubstituted aromatic rings or heterocyclic base group；

R²Selected from H, D, straight chained alkyl with 1 to 20 C atom, alkoxy with 1 to 20 C atom, thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl with 3 to 20 C atoms, branch or cricoid alkoxy with 3 to 20 C atoms, branch or cricoid thio alkoxy group with 3 to 20 C atoms, silyl-group, substituted keto group with 1 to 20 C atom, alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF₃One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of.

Application of the above-mentioned organic compound in organic electronic device.

A kind of polymer, at least one repetitive unit includes above-mentioned organic compound in the polymer.

A kind of organic mixture for organic electronic device, the organic mixture include at least one organic functional material and above-mentioned organic compound；The organic functional material is selected from hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electron transport material, electron-blocking materials, organic host material or luminescent material.

A kind of composition, including organic solvent and above-mentioned organic compound or above-mentioned polymer.

Perhaps above-mentioned organic mixture or the functional layer are prepared by above-mentioned composition for a kind of organic electronic device, including functional layer, the above-mentioned organic compound of functional layer or above-mentioned polymer.

The details of one or more embodiments of the invention proposes in following attached drawing and description.Other features, objects, and advantages of the present invention will become obvious from specification, attached drawing and claims.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not intended to limit the present invention.

Herein, composition, printing ink and ink have the same meaning, and can be interchanged between them.Material of main part, host material, Host material and Matrix material have the same meaning, and can be interchanged between them.Metallo-organic complex, metal organic complex and organometallic complex have the same meaning, and can be interchanged between them.

Shown in the structure such as general formula (1) of the organic compound for organic electronic device of one embodiment:

Wherein,

R²Selected from H, D, straight chained alkyl with 1 to 20 C atom, alkoxy with 1 to 20 C atom, thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl with 3 to 20 C atoms, branch or cricoid alkoxy with 3 to 20 C atoms, branch or cricoid thio alkoxy group with 3 to 20 C atoms, silyl-group, substituted keto group with 1 to 20 C atom, alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group with 7 to 20 C atoms, cyano group (- CN), carbamoyl group (- C (=O) NH₂), halogen formyl group (- C (=O)-X, wherein X represents halogen atom), formyl group (- C (=O)-H), isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF₃One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of；R²Monocycle or polycyclic aliphatic series or the multiple R of aromatic ring are formed with the ring of the group bonding²Monocycle or polycyclic aliphatic series or aromatic ring are formed between each other.

It should be noted that Ar²Ring on the position that may replace can be by R¹Replace or unsubstituted, works as R¹It may be the same or different when repeatedly occurring.

Above-mentioned organic compound includes at least two spirane structure units, has thermal excitation delayed fluorescence luminous (TADF) special Property.Organic compound according to the invention can be used as TADF luminescent material, by cooperating with suitable material of main part, its luminous efficiency and service life as electroluminescent device can be improved, provides that a kind of manufacturing cost is low, high-efficient, the service life is long, the solution of the low luminescent device to roll-off.

Ar in one of the embodiments,¹-Ar²Independently selected from unsubstituted or by R¹Substituted aromatic hydrocarbon or heteroaryl perfume (or spice) cyclic hydrocarbon system.

Ar in one of the embodiments,¹-Ar²Independently selected from unsubstituted or by R¹The aromatic ring or heteroaromatic ring with 2-20 carbon atom replaced.

Z is selected from two bridges or three bridging bases in one of the embodiments,.

Z is selected from the three bridging bases for including following any structure formula in one of the embodiments,.

Wherein, R₄、R₅With R₆Independently selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR³)₂、Si(R³)₃, linear paraffin, alkane ether, containing 1~10 carbon atom alkane thioether, branched paraffin, cycloalkane or contain 3~10 The alkane ether group of a carbon atom；Dotted line key indicates any three abutment and structural unit Ar¹、Ar²Or the key of the C bonding on phenyl ring.

Z three bridging bases shown in any structure formula in above-mentioned table in one of the embodiments,.

Ar in one of the embodiments,²It is not present, Z is selected from the two bridging bases for including following any structure formula.

Wherein, R₄、R₅Independently selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR³)₂、Si(R³)₃, linear paraffin, alkane ether, containing 1~10 carbon atom alkane thioether, branched paraffin, cycloalkane or alkane ether group containing 3~10 carbon atoms；Dotted line key indicates any two abutment and structural unit Ar¹Or the key of the C bonding on phenyl ring.

Y in one of the embodiments,₁And Y₂In at least one be C.Y in one of the embodiments,₁And Y₂It is selected from C；

Ar in one of the embodiments,¹Selected from aromatic series, heteroaromatic or non-aromatic ring system with 5-20 carbon atom.

Ar in one of the embodiments,¹Selected from aromatic series or heteroaromatic with 5-20 carbon atom.Further, in one embodiment, Ar¹Selected from aromatic series or heteroaromatic with 5-18 carbon atom.Ar¹Selected from aromatic series or heteroaromatic with 5-16 carbon atom.Ar¹Selected from aromatic series or heteroaromatic with 5-13 carbon atom.

Ar in one of the embodiments,²Selected from aromatic series or heteroaromatic with 5-60 carbon atom.Ar in one of the embodiments,²Selected from aromatic series or heteroaromatic with 5-50 carbon atom.Ar in one of the embodiments,²Selected from aromatic series or heteroaromatic with 5-40 carbon atom.Ar in one of the embodiments,²Selected from aromatic series or heteroaromatic with 5-25 carbon atom.

For the purpose of the present invention, aromatic ring includes 6 or more annular atoms in ring system.For miscellaneous aromatic ring comprising 5 or more annular atoms and at least one hetero atom in ring system, condition is that carbon atom and heteroatomic sum are at least 4.Hetero atom is selected from one of Si, N, P, O, S and Ge or a variety of.Hetero atom is selected from one of Si, N, P, O and S or a variety of in one of the embodiments,.It should be noted that aromatic series or heteroaromatic ring system not only include the system of aromatic radical or heteroaryl perfume base, moreover, plurality of aryl or heteroaryl can also be interrupted (< 10% non-H atom, such as C, N or O atom) by short non-aromatic unit.Multiple aryl or heteroaryl can also be interrupted (less than the non-H atom of 10% atomicity accounting) by short non-aromatic unit in one of the embodiments,., 9 '-spiral shell, two fluorenes, 9,9- diaryl fluorenes, triaryl amine, the systems such as diaryl ether, for the goal of the invention it also hold that being aromatic ring system.

For the purpose of the present invention, non-aromatic ring system includes 1-10 carbon atom in ring system, and not only including saturation but also including the unsaturated cyclic annular system in part, they can be unsubstituted or by group R¹Single or multiple substitution, group R¹It can be same or different in occurring each time.Non-aromatic ring system includes 1-3 carbon atom in ring system in one of the embodiments,.Non-aromatic ring system can also include one or more hetero atoms in one of the embodiments,.Wherein, hetero atom can be selected from one of Si, N, P, O, S and Ge or a variety of.Hetero atom is selected from one of Si, N, P, O and S or a variety of in one of the embodiments,.These for example can be class cyclohexyl or class piperidines system, be also possible to class cyclo-octadiene ring-type system.The term is equally applicable to condensed non-aromatic ring system.

For the purpose of the present invention, the wherein H atom on NH or bridging base CH₂Group can be by R¹Group replaces.R in one of the embodiments,¹It is selected from: (1) C1~C10 alkyl, wherein, C1-C10 alkyl can refer to following group: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, 2- methyl butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl, 2- ethylhexyl, trifluoromethyl, five methyl fluorides, 2, 2, 2- trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl group, heptenyl, cycloheptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base or octynyl；(2) C1~C10 alkoxy, wherein C1~C10 alkoxy can be with nail oxygroup, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2- methyl butoxy；(3) C2 to C10 aryl or heteroaryl, depending on purposes, it can be monovalence or divalent, can also be replaced by the above-mentioned group R1 referred in each case and can be connect by any desired position with aromatic series or miscellaneous aromatic rings.In one of the embodiments, C2 to C10 aryl or heteroaryl are selected from following group: benzene, naphthalene, anthracene, pyrene, dihydropyrene, it bends, Asia puecon, firefly anthracene, naphthacene, pentacene, BaP, furans, benzofuran, isobenzofuran, dibenzofurans, thiophene, benzothiophene, isothiophene, dibenzothiophen, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo -5, 6- quinoline, benzo -6, 7- quinoline, benzo -7, 8- quinoline, phenthazine, phenoxazine, pyrazoles, indazole, imidazoles, benzimidazole, naphtho- imidazoles, phenanthro- imidazoles, pyridine-imidazole, pyrazine and imidazoles, quinoxaline and imidazoles, oxazole, benzoxazoles, aphthoxazoles, anthra oxazole, phenanthro- oxazole, isoxazole, 1, 2- thiazole, 1, 3- thiazole, benzothiazole, pyridazine, Benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, pyrazine, phenazine, 1,5- benzodiazine, nitrogen carbazole, benzo carboline, phenanthroline, 1,2,3- triazole, 1,2,4- triazole, benzotriazole, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazine, 1,2,4- triazine, 1,2,3- triazine, tetrazolium.1,2,4,5- tetrazine, 1,2,3,4- tetrazine, 1,2,3,5- tetrazine, purine, pteridine, indolizine or diazosulfide.For purposes of the present invention, fragrant and heteroaromatic ring system thinks especially in addition to the above-mentioned aryl and heteroaryl referred to, also refers to biphenylene, sub- terphenyl, fluorenes, two fluorenes of spiral shell, dihydro phenanthrene, tetrahydro pyrene and cis or trans indenofluorene.

Ar in one of the embodiments,¹With Ar²Independently selected from fragrant, the heteroaromatic perhaps non-aromatic ring system with 5 or more carbon atoms, they can be unsubstituted or by one or two R¹Group replaces.Aromatic ring or heteroaromatic ring system are selected from benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene in one of the embodiments,.

Ar in one of the embodiments,¹Or Ar², especially Ar¹It include following any structure formula.Following any structure formula may be by one or more group R¹Replace.

Wherein, X₁Selected from CR⁷Or N；Y is selected from CR⁸R⁹、SiR¹⁰R¹¹、NR¹², C (=O), S or O；

R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²Independently selected from H, D, straight chained alkyl with 1 to 20 C atom, alkoxy with 1 to 20 C atom, thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl with 3 to 20 C atoms, branch or cricoid alkoxy with 3 to 20 C atoms, branch or cricoid thio alkoxy group with 3 to 20 C atoms, branch or cricoid silyl-group with 3 to 20 C atoms, substituted keto group with 1 to 20 C atom, alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanic acid Ester group, hydroxyl group, nitryl group, CF₃Group, Cl, Br, F, crosslinkable group, the substitution with 5 to 40 annular atoms Or one of unsubstituted aromatics or heteroaromatic ring system, the aryloxy group with 5 to 40 annular atoms or heteroaryloxy group or a variety of；R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²In at least one ring for being bonded with the building stone form monocycle or polycyclic aliphatic series or aromatic ring or R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²In at least two be mutually bonded to form monocycle or polycyclic aliphatic series or aromatic ring.

It should be noted that Ar¹Selected from following any group.

Ar in one of the embodiments,¹Or Ar², especially Ar¹It include following structural formula.Following any structure formula can be further by one or more group R₁Replace.

Y in one of the embodiments,₁And Y₂It is both selected from C, Ar¹For phenyl.

Ar in one of the embodiments,²Include following structural unit or their combination.

Wherein, n is 1,2,3 or 4.

Further, Ar in one of the embodiments,²Any group in above-mentioned table.

Organic compound triplet T with higher in one of the embodiments,₁, T₁ 2.0eV.T in one of the embodiments,₁≥2.2eV.Further, in one embodiment, T₁≥2.4eV.T in one of the embodiments,₁≥2.6eV.T1 >=2.8eV in one of the embodiments,.

In general, the triplet T1 of organic compound depends in compound the separation structure with maximum conjugated system.Generally, T1 successively decreases with the increase of conjugated system.Molecular structure shown in the following general formula (1a) in chemical formula (1) has maximum conjugated system in one of the embodiments,.

For general formula (1a) in the case where removing substituent group, carbon atom number is no more than 30 in one of the embodiments,.For general formula (1a) in the case where removing substituent group, carbon atom number is no more than 26 in one of the embodiments,.For general formula (1a) in the case where removing substituent group, carbon atom number is no more than 22 in one of the embodiments,.For general formula (1a) in the case where removing substituent group, carbon atom number is no more than 20 in one of the embodiments,.

General formula (1a) triplet T with higher in one of the embodiments,₁, T₁ 2.0eV.T in one of the embodiments,₁ 2.2eV.T in one of the embodiments,₁ 2.4eV.T in one of the embodiments,₁ 2.6eV.T in one of the embodiments,₁ 2.8eV。

Compound according to the invention, convenient for obtaining thermal excitation delayed fluorescence TADF characteristic.According to the principle of thermal excitation delayed fluorescence TADF material (referring to Adachi et al., Nature Vol 492,234, (2012)), as the Δ E (S of organic compound₁-T₁) it is sufficiently small when, the triplet excitons of the organic compound can be by reversed internal conversion to singlet exciton, to realize High Efficiency Luminescence.Wherein, Δ E (S₁-T₁) indicate the first triplet excited state T of the organic compound₁With its first singlet excited S₁Between energy level difference.In general, TADF material is connected by supplied for electronic (Donor) with electron deficient or electrophilic (Acceptor) group, that is, has apparent D-A structure.

Δ E (the S of the organic compound in one of the embodiments,₁-T₁)≤0.30eV.Δ E (the S of the organic compound in one of the embodiments,₁-T₁)≤0.25eV.Δ E (the S of the organic compound in one of the embodiments,₁-T₁)≤0.20eV.Δ E (the S of the organic compound in one of the embodiments,₁-T₁)≤0.10eV。

In one of the embodiments, according to the organic compound of general formula (1), wherein Ar²Comprising electron-donating group or include electron-withdrawing group.

The electron-donating group includes following group in one of the embodiments,.

Electron-donating group any group in table as above in one of the embodiments,.

In one of the embodiments, the electron-withdrawing group be selected from F, cyano or include following any group structural formula.

Wherein, 1,2 or 3 n；X1-X8 is independently selected from CR¹³Or N, and X¹-X⁸In at least one be N；R¹³Selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl.

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

It is not polymer, oligomer, the molecule of dendritic or blend that term " small molecule " as defined herein, which refers to,.In particular, there is no repetitive structure in small molecule.Molecular weight≤4000 gram/mol of small molecule.Further, molecular weight≤3000 gram/mol of small molecule.Further, molecular weight≤2000 gram/mol of small molecule.

High polymer, i.e. Polymer, including homopolymer (homopolymer), copolymer (copolymer), block copolymer (block copolymer).In addition in the present invention, high polymer also includes tree (dendrimer), synthesis and application in relation to tree refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.].

Conjugated highpolymer (conjugated polymer) is a high polymer, its main chain backbone is mainly the sp by C atom²Hybridized orbit is constituted, and famous example has: polyacetylene polyacetylene and poly (phenylene vinylene), and the C atom on main chain can also be replaced by other non-C atoms, and as the sp on main chain²When hydridization is interrupted by some natural defects, it is still considered as being conjugated highpolymer.In addition in the present invention conjugated highpolymer also include include arylamine (aryl amine), aryl hydrogen phosphide (aryl phosphine) and other heterocyclic arenes (heteroarmotics), metal-organic complex (organometallic complexes) etc. on main chain.

Especially by the substituent group on general formula (1) unit and optionally on existing benzene ring units, two spirane structures make molecule have biggish rigid structure, ensure that the solubility of organic micromolecule compound.If Ar²There are other substituent groups such as alkane group, these substituent groups can also promote solubility.

Depending on substitution pattern, the structural unit of general formula (1) is suitable for the various functions in organic micromolecule compound.Therefore, they preferably can be used as the main skeleton of small molecule compound or as illuminator.Especially by group Ar²Which compound is described especially suitable for which function.Ar²The characteristic electron of mutual-through type (1) unit has an impact.

H in one of the embodiments, on organic compound is at least partly deuterated.10% H is deuterated in one of the embodiments,.20% H is deuterated in one of the embodiments,.30% H is deuterated in one of the embodiments,.40% H is deuterated in one of the embodiments,.

Organic compound shown in general formula (1) is selected from one of following any structure formula compound represented in one of the embodiments,.These structures can be substituted on the point that all possibility replace.

The application of above-mentioned organic compound in the mixture.

The application of above-mentioned organic compound in the composition.

The polymer of one embodiment, at least one repetitive unit include just like organic compound shown in general formula (1).The polymer is non-conjugated polymer in one of the embodiments, wherein the structural unit as shown in general formula (1) is on side chain.In other embodiments, which is conjugated polymer.

The application of above-mentioned polymer in the composition.Above-mentioned polymer can application in the mixture.Above-mentioned polymer can also be applied in organic electronic device.

The organic mixture of one embodiment includes above-mentioned organic compound, and at least also comprising another organic functional material.Wherein, organic functional material is selected from hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host material (Host), singlet emitters (fluorescent illuminant), weight state illuminator (phosphorescent emitter) or organic thermal excitation delayed fluorescence material (TADF material).Organic thermal excitation delayed fluorescence material can be luminescent organometallic complex compound.Such as various organic functional materials are described later in detail in WO2010135519A1, US2009 0134784A1 and WO 2011110277A1, the full content in this 3 patent document is incorporated herein by reference hereby.Organic functional material can be small molecule or high polymer material.

The organic mixture includes above-mentioned organic compound and a kind of phosphorescent emitter in one of the embodiments,.Here organic compound according to the invention can be used as main body, at this point, phosphorescent emitter weight percent≤30wt%.In implementing at wherein one, phosphorescent emitter weight percent≤25wt%.In implementing at wherein one, phosphorescent emitter weight percent≤20wt%.

The organic mixture includes above-mentioned organic compound and a kind of material of main part in one of the embodiments,.Here organic compound according to the invention can be used as luminescent material, at this point, weight percent≤30wt% of organic compound.Weight percent≤25wt% of organic compound in one of the embodiments,.Weight percent≤20wt% of organic compound in one of the embodiments,.Weight percent≤15wt% of organic compound in one of the embodiments,.

The organic mixture includes above-mentioned organic compound, a kind of phosphorescent emitter and a kind of material of main part in one of the embodiments,.In one embodiment, organic compound according to the invention can be used as auxiliary light emission material, and the weight ratio with phosphorescent emitter is from 1:2 to 2:1.In another embodiment, the T of organic compound according to the invention₁Higher than phosphorescence The T of illuminator₁。

The organic mixture includes above-mentioned organic compound and another kind TADF material in one of the embodiments,.

Some more detailed descriptions (but not limited to this) are made to material of main part, phosphorescent light-emitting materials and TADF material below.

1. triplet material of main part (Triplet Host):

The example of triplet material of main part is not particularly limited, and any metal complex or organic compound may all be used as main body, as long as its triplet energy ratio illuminator, especially triplet emitters or phosphorescent emitter are higher.The example that can be used as the metal complex of triplet main body (Host) includes but is not limited to following general structure:

M is metal；(Y³-Y⁴) it is one liang of tooth ligand, Y³And Y⁴Independently selected from C, N, O, P or S；L is an assistant ligand；M is an integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.

The metal complex that can be used as triplet main body in one of the embodiments, has following form:

Wherein, (O-N) is one liang of tooth ligand, wherein metal and O and N Atomic coordinate.

M is selected from Ir or Pt in one of the embodiments,.

The example of the organic compound of triplet main body be can be used as selected from the compound for including aromatic hydrocarbon ring base, such as benzene, biphenyl, triphenyl, benzo, fluorenes；It or include the compound of fragrant heterocyclic radical, such as dibenzothiophenes, dibenzofurans, dibenzo selenophen, furans, thiophene, benzofuran, benzothiophene, benzo selenophen, carbazole, indole carbazole, pyridine indoles, two pyridine of pyrroles, pyrazoles, imidazoles, triazole type, oxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, oxazole, dibenzo oxazole, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, two pyridine of benzo selenophen pyridine and selenophen benzo；It or include the group of 2 to 10 ring structures, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and link together directly with one another or by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be further substituted, and substituent group is selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl.

In one of the embodiments, triplet material of main part is selected from the compound comprising at least one following group:

Wherein, R¹-R⁷Independently selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl, when they are aryl or heteroaryl, they and above-mentioned Ar¹And Ar²Meaning is identical；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；X¹-X⁸Selected from CH or N, X⁹Selected from CR¹R²Or NR¹。

The example of suitable triplet material of main part is listed in following table.

2, phosphorescent light-emitting materials

Phosphorescent light-emitting materials are also referred to as triplet emitters.In a preferential embodiment, triplet emitters are the metal complexes for having formula M (L) n.Wherein M is a metallic atom；It can be identical or different when L occurs every time, be an organic ligand, it passes through, and one or more positions are bonded or coordination is connected on metallic atom M；N is an integer greater than 1, and preferably choosing is 1,2,3,4,5 or 6.These metal complexes are connected on a polymer by one or more positions in one of the embodiments, preferably by organic ligand.

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

Triplet emitters include cheland in one of the embodiments, i.e. ligand, are coordinated by least two binding sites and metal.Triplet emitters include two or three identical or different bidentates or multidentate ligand in one of the embodiments,.Cheland is conducive to improve the stability of metal complex.

The example of organic ligand is selected from phenylpyridine derivative, 7,8- benzoquinoline derivative, 2 (2- thienyl) pyridine derivates, 2 (1- naphthalene) pyridine derivates or 2 phenylchinoline derivatives.All these organic ligands may be all substituted, such as be replaced by fluorine-containing or trifluoromethyl.Assistant ligand can be selected from acetic acid acetone or picric acid.

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

Wherein M is metal, is selected from transition metal element, lanthanide series or actinides.

Ar¹For cyclic group, identical or different, and Ar can be when occurring every time¹Including at least there is a donor atom, that is, there is the atom of a lone pair electrons, such as nitrogen or phosphorus, is connected by its cyclic group and metal coordination；Ar²For cyclic group, identical or different, Ar can be when occurring every time²Including at least there is a C atom, it is connect by its cyclic group with metal；Ar¹And Ar²It is linked together by covalent bond, can respectively carry one or more substituent groups, they can also be linked together by substituent group again；It can be identical or different when L occurs every time, L is assistant ligand, is preferable over double-tooth chelate ligand, preferably monoanionic, bidentate cheland；M is selected from 1,2 or 3；N is selected from 0,1 or 2.L is double-tooth chelate ligand in one of the embodiments,.L is monoanionic, bidentate cheland 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 0 in one of the embodiments,.

The example that the material of some triplet emitters is extremely applied can be found in following patent documents and document: 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 2010099 20070087219 A1 of 852, WO 2010102709, US, 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.C Hem.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 full content in the above-mentioned patent document and document listed is incorporated herein by reference hereby.

3, TADF material

Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, and the internal quantum efficiency of device is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, it can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, the internal quantum efficiency of device is made to reach 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its application in OLED.Hot activation delayed fluorescence luminescent material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material generally has small singlet-triplet poor (Δ Est), triplet excitons can by it is counter be between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation.Device internal quantum efficiency can reach 100%.Material structure is controllable simultaneously, and property is stablized, cheap woth no need to noble metal, in having a extensive future for the field OLED.

TADF material needs to have lesser singlet-triplet poor.Δ Est < 0.3eV in one of the embodiments,.Δ Est < 0.2eV in one of the embodiments,.Δ Est < 0.1eV in one of the embodiments,.TADF material has smaller Δ Est in one of the embodiments,.In another embodiment, TADF has preferable fluorescence quantum efficiency.Some TADF luminous material can be found in 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.Le Tt., 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., 48,2012,9 580, Adachi, et.al.Chem.Commun., 48,2013,10385, Adachi, et.al.Adv.Mater., 25,2013,3319, Adachi, et.al.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.C Hem.A., 117,2013,5607, the full content in the above-mentioned patent listed or article file is incorporated herein by reference hereby.

The example of some suitable TADF luminescent materials is listed in following table.

Above-mentioned organic compound is for printing OLED, molecular weight >=700g/mol in one of the embodiments,.Molecular weight >=800g/mol of organic compound in one of the embodiments,.Molecular weight >=900g/mol of organic compound in one of the embodiments,.Molecular weight >=1000g/mol of organic compound in one of the embodiments,.Molecular weight >=1100g/mol of organic compound in one of the embodiments,.

Above-mentioned organic compound or organic mixture in one of the embodiments, solubility >=10mg/ml at 25 DEG C, in toluene.Solubility >=15mg/ml in toluene in one of the embodiments,.Solubility >=20mg/ml in toluene in one of the embodiments,.

Application of the above-mentioned organic mixture in organic electronic device.

The organic mixture of another embodiment includes above-mentioned polymer, and described in the organic mixture about an embodiment as above such as the various components of the organic mixture and content, details are not described herein.

The composition of one embodiment includes organic solvent and above-mentioned organic compound or polymer.In the present embodiment, composition is ink.When being used for printing technology to the composition, the viscosity of ink, surface tension is important parameter.The surface tension parameter of suitable ink is suitable for specific substrate and specific printing process.

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

In one embodiment, viscosity of the ink at operating temperature or 25 DEG C is in 1cps to 100cps range.In one of the embodiments, ink in the viscosity at operating temperature or 25 DEG C viscosity of the ink at operating temperature or 25 DEG C in one of the embodiments, in 1cps to 50cps range.Viscosity of the ink at operating temperature or 25 DEG C is in 1.5cps to 20cps range in one of the embodiments,.Viscosity of the ink at operating temperature or 25 DEG C is in 4.0cps to 20cps range in one of the embodiments,.The ink jet printing so that the composition is more convenient for.

Viscosity can be adjusted by different methods, as chosen the concentration with functional material in ink by suitable solvent.It include that the ink of metal organic complex or high polymer can facilitate people that will print ink to adjust according to printing process used in range appropriate.The weight ratio for the organic functional material for including in composition is 0.3%~30wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 0.5%~20wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 0.5%~15wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 0.5%~10wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 1%~5wt%.

In one embodiment, organic solvent includes the first solvent, which is selected from based on aromatics and/or heteroaromatic solvent.Further, which can be aliphatic chain/cyclosubstituted arsol or aromatics ketone solvent or aromatics Ether solvents.

The example of first solvent has, but it is not limited to: based on aromatics or heteroaromatic solvent: to diisopropyl benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, 1, 4- dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, diamyl benzene, 3 penta benzene, amyl toluene, ortho-xylene, meta-xylene, paraxylene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1, 2, 3, 4- durene, 1, 2, 3, 5- durene, 1, 2, 4, 5- durene, butylbenzene, detergent alkylate, dihexyl benzene, dibutyl benzene, to diisopropyl benzene, 1- methoxynaphthalene, cyclohexyl benzene, dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, 1- methyl naphthalene, 1, 2, 4- trichloro-benzenes, 1, 3- dipropoxy benzene, 4, 4- difluoro-diphenylmethane, 1, 2- dimethoxy-4 ' (1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, N- methyldiphenylamine, 4- isopropyl biphenyl, α, α-dichloro diphenyl methane, 4- (3- phenyl propyl) pyridine, Ergol, 1, bis- (3,4- 3,5-dimethylphenyl) ethane of 1-, 2- isopropyl naphthalene, benzyl ether etc.；Solvent based on ketone: 1-tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxyl group) tetralone, acetophenone, propiophenone, benzophenone and their derivative, such as 4- methyl acetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- methyl phenyl ketone, 3- methyl phenyl ketone, 2- methyl phenyl ketone, isophorone, 2,6,8- trimethyl -4- nonanone, fenchone, methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, phorone, two n-pentyl ketone；Aromatic ether solvents: 3- phenoxytoluene, butyl phenyl ether, benzyl butyl benzene, p-anisaldehyde dimethyl-acetal, tetrahydro -2- phenoxy group -2H- pyrans, 1, 2- dimethoxy-4 '-(1- acrylic) benzene, 1, 4- benzdioxan, 1, 3- dipropyl benzene, 2, 5- dimethoxy-p, this ether of 4- ethyl, 1, 2, 4- trimethoxy-benzene, 4- (1- acrylic) -1, 2- dimethoxy benzene, 1, 3- dimethoxy benzene, glycidyl phenyl ether, dibenzyl ether, 4- tert-butyl anisole, trans--anethole, 1, 2- dimethoxy benzene, 1- methoxynaphthalene, diphenyl ether, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, amyl ether c hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl Ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether；Ester solvent: sad alkyl ester, decanedioic acid alkyl ester, stearic acid alkyl ester, benzoic acid alkyl esters, phenylacetic acid alkyl ester, cinnamic acid alkyl ester, oxalic acid alkyl ester, maleic acid alkyl ester, alkane lactone, oleic acid alkyl ester etc..

Further, which is also selected from aliphatic ketone, for example, methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, 2,6,8- trimethyl -4- nonanones, phorone, two n-pentyl ketone etc.；Or fatty ether, for example, one of amyl ether, hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethyleneglycol dimethyl ether or a variety of.

In one embodiment, the organic solvent further includes the second solvent, second solvent is selected from methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, 1, 4 dioxanes, acetone, methyl ethyl ketone, 1, 2 dichloroethanes, 3- phenoxytoluene, 1, 1, 1- trichloroethanes, 1, 1, 2, 2- tetrachloroethanes, ethyl acetate, butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, one of naphthalane and indenes are a variety of.

In one embodiment, the composition can be solution or suspension.This is determined according to the compatibility between organic mixture and organic solvent.

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

In one embodiment, above-mentioned composition is preparing the application in organic electronic device.In particular, the purposes as coating or printing ink when preparing organic electronic device, particularly preferably passes through the preparation method of printing or coating.

Wherein, suitable printing or coating technique include but is not limited to inkjet printing, spray printing (Nozzle Printing), typographic printing, silk-screen printing, dip-coating, rotary coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing or the coating of slit-type squash type etc..Preferably intaglio printing, spray printing and ink jet printing.The composition can also include component example, and lid component example is selected from one of surface active cpd, lubricant, wetting agent, dispersing agent, hydrophobing agent and bonding agent or a variety of, so as to which for adjusting viscosity, filming performance is improved attached Property etc..Related printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan chief editor " print media handbook: technology and production method " (Handbook of Print Media:Technologies and Production Methods), ISBN 3-540-67326-1.

In one embodiment, the organic compound or high polymer are applied to organic electronic device by the application of above-mentioned organic compound or high polymer in organic electronic device.The organic electronic device can be selected from Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED), organic photovoltaic battery (Organic Photovoltage, OPV), organic light emission battery (OLEEC), organic field-effect tube (organic field2effect transistor, OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode).In one embodiment, organic electronic device is electroluminescent device, such as OLED, OLEEC and organic light-emitting field effect pipe.Further, which is used for the luminescent layer of electroluminescent device.

The organic electronic device of one embodiment includes at least one above-mentioned organic compound or organic mixture.Wherein, organic electronic device may include cathode, anode and the functional layer between cathode and anode, which includes that above-mentioned organic compound or above-mentioned polymer or above-mentioned organic mixture or the functional layer are prepared by above-mentioned composition.Specifically, organic electronic device includes at least cathode, anode and a functional layer between cathode and anode, functional layer includes at least a kind of above-mentioned organic compound or above-mentioned polymer or above-mentioned organic mixture or the functional layer is prepared by above-mentioned composition.Functional layer is selected from the one or more of hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, electronic barrier layer and luminescent layer.

The organic electronic device can be selected from Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED), organic photovoltaic battery (Organic Photovoltage, OPV), organic light emission battery (OLEEC), organic field-effect tube (organic field2effect transistor, OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode).In one embodiment, which is organic electroluminescence device, such as OLED, OLEEC or organic light-emitting field effect pipe.Further, Organic Light Emitting Diode can be vapor deposition type Organic Light Emitting Diode or printed form Organic Light Emitting Diode.

In one embodiment, the luminescent layer of organic electroluminescence device includes a kind of above-mentioned organic compound or high polymer, or include a kind of above-mentioned organic compound or high polymer and a kind of phosphorescent emitter, or comprising a kind of above-mentioned organic compound or high polymer and a kind of material of main part, or include a kind of above-mentioned organic compound or high polymer, a kind of phosphorescent emitter and a kind of material of main part.

In one embodiment, organic electroluminescence device includes the substrate stacked gradually, anode, luminescent layer and cathode.Wherein, the number of plies of luminescent layer is at least one layer.

Substrate can be opaque or transparent.Transparent substrate can be used to manufacture a transparent light emitting component, refer to the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996, and 68, p2606.Substrate can be rigid or elasticity.Substrate is also possible to plastics, metal, semiconductor wafer or glass.Preferably, substrate has smooth surface.Substrate free of surface defects is especially desirable selection.In an embodiment, substrate is flexible, optional in thin polymer film or plastics, and glass transition temperature Tg is 150 DEG C or more.Flexible base board can be poly- (ethylene glycol terephthalate) (PET) or polyethylene glycol (2,6- naphthalene) (PEN).The glass transition temperature Tg of substrate is 200 DEG C or more in one of the embodiments,.The glass transition temperature Tg of substrate is 250 DEG C or more in one of the embodiments,.The glass transition temperature Tg of substrate is 300 DEG C or more in one of the embodiments,.

Anode may include conductive metal or metal oxide or conducting polymer.Anode can be easily injected into hole into hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one embodiment, the absolute value of the difference of the HOMO energy level or valence-band level of the illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.5eV.The absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.3eV.The absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.2eV.The example of anode material includes but is not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO and aluminium-doped zinc oxide (AZO) Deng.Anode material can also be with other materials.Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc. can be used in anode material.In other embodiments, anode is patterning.Patterned ITO electrically-conductive backing plate is commercially available, and can be used to prepare the organic electronic device according to the present embodiment.

Cathode may include conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or directly into luminescent layer.In one embodiment, the absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.5eV in the work function of cathode and luminescent layer.The absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.3eV in the work function and luminescent layer of cathode.The absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.2eV in the work function and luminescent layer of cathode.The material of all cathodes that can be used as OLED all may be as the cathode material of the organic electronic device of the present embodiment.The example of cathode material includes but is not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation and electron beam (e-beam) etc. can be used in cathode material.

OLED can also include other function layer, such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), electron injecting layer (EIL), electron transfer layer (ETL) or hole blocking layer (HBL).It is described later in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1 suitable for the material in these functional layers, is hereby incorporated herein by reference the full content in this three piece patent documents.

The luminescent layer of organic electroluminescence device is prepared by above-mentioned composition in one of the embodiments,.

In one embodiment, the emission wavelength of the organic electroluminescence device luminescent device is 300 between 1000nm.The emission wavelength of organic electroluminescence device luminescent device is 350 between 900nm in one of the embodiments,.The emission wavelength of organic electroluminescence device luminescent device is 400 between 800nm in one of the embodiments,.

In one embodiment, the application of above-mentioned organic electronic device in the electronic device.Electronic equipment is selected from display equipment, lighting apparatus, light source or sensor.Wherein, organic electronic device can be organic electroluminescence device.

A kind of electronic equipment, including above-mentioned organic electronic device.

Below in conjunction with preferred embodiment, the present invention is described, but the present invention is not limited to the following examples, it should be understood that, appended claims summarise the scope of the present invention under the guidance of present inventive concept it should be appreciated by one skilled in the art that, to certain change that various embodiments of the present invention are carried out, will all be covered by the spirit and scope of claims of the present invention.

Embodiment 1

Two spiral shell of 5'- ([1,1':3', 1 "-triphenyl] -5'-yl) -5'H- [fluorenes -9,7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes]

5.70g, [fluorenes -9,7'- naphtho- [2, the 3-b] carbazole -12' of 10mmol 5'H- spiral shell two are added in the three-necked flask of 250ml, 9 "-fluorenes], 3.41g, 11mmol 5'- bromo- 1,1':3', 1 "-triphen, 2.76g, 20mmol potassium carbonate, 0.22g, 1mmol Pd (OAc)₂, P (t-Bu)₃1ml and 100ml dry toluene, in N₂In atmosphere, it is heated to back flow reaction and stays overnight, TLC tracking reaction Process is down to room temperature to the end of reacting.Methylene chloride 200ml is added, is washed with water three times, merges organic phase, sodium sulphate is added to dry, filter, revolving does organic solvent therein, obtain SOLID ORGANIC product solid product, with methylene chloride, ethyl alcohol recrystallization, product white solid powder 5'- ([1,1':3' is obtained, 1 "-triphenyl] -5'-yl) two spiral shell of -5'H- [fluorenes -9; 7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes].MS (ASAP)=797.4.

Embodiment 2

5'- (4,6- diphenyl -1,3,5- triazine -2-yl) -5'H- spiral shell two [fluorenes -9,7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes

5.70g, two [fluorenes -9,7'- naphtho- [2 of 10mmol 5'H- spiral shell are added in the three-necked flask of 250ml, 3-b] carbazole -12', 9 "-fluorenes], 0.5g, 20mmol sodium hydride; the dry DMF of 100ml; stir 30 minutes at room temperature, solution becomes brown, and 2.97g is added dropwise; 11mmol 2- chloro- 4; 6- diphenyl -1,3,5-triazines DMF solution, in N₂In atmosphere, continue stirring 4 hours, TLC tracks reaction process, to the end of reacting, with water slowly quenching reaction.Methylene chloride 200ml is added, is washed with water three times, merges organic phase, sodium sulphate is added to dry, filter, revolving does organic solvent therein, SOLID ORGANIC product solid product is obtained, is recrystallized with methylene chloride, petroleum ether, obtains product white solid powder 5'- (4,6- diphenyl -1,3,5- triazine -2-yl) [fluorenes -9, the 7'- naphtho- [2 of -5'H- spiral shell two, 3-b] carbazole -12', 9 "-fluorenes.MS (ASAP)=800.2.

Embodiment 3

Two spiral shell of 5'- (4- (9H- carbazole -9-yl) phenyl) -5'H- [fluorenes -9,7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes]

5.70g, two [fluorenes -9,7'- naphtho- [2 of 10mmol 5'H- spiral shell are added in the three-necked flask of 250ml, 3-b] carbazole -12', 9 "-fluorenes], 3.54g, 11mmol 9- (4- bromophenyl) -9H- carbazole, 2.76g; 20mmol potassium carbonate, 0.22g, 1mmol Pd (OAc)₂, P (t-Bu)₃1ml and 100ml dry toluene, in N₂It in atmosphere, is heated to back flow reaction and stays overnight, TLC tracking reaction process is down to room temperature to the end of reacting.Methylene chloride 200ml is added, it is washed with water three times, merge organic phase, sodium sulphate is added and dries, filters, revolving does organic solvent therein, it obtains SOLID ORGANIC product solid product and obtains two spiral shell [fluorenes -9 of product white solid powder 5'- (4- (9H- carbazole -9-yl) phenyl) -5'H- with methylene chloride, ethyl alcohol recrystallization, 7'- naphtho- [2,3-b] carbazole - 12', 9 "-fluorenes].MS (ASAP)=810.4.

Embodiment 4

Two spiral shell of 5'- (3- (4,6- diphenyl -1,3,5- triazine -2-yl) phenyl) -5'H- [fluorenes -9,7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes]

In the present embodiment, final product 5'- (3- (4, 6- diphenyl -1, 3, 5- triazine -2-yl) phenyl) two spiral shell [fluorenes -9 of -5'H-, 7'- naphtho- [2, 3-b] carbazole -12', 9 "-fluorenes] with embodiment 3 in two spiral shell [fluorenes -9 of product 5'- (4- (9H- carbazole -9-yl) phenyl) -5'H-, 7'- naphtho- [2, 3-b] carbazole -12', 9 "-fluorenes] synthesis step it is identical, except that intermediate is replaced with 2- (3- bromophenyl) -4 by 9- (4- bromophenyl) -9H- carbazole, 6- diphenyl -1, 3, 5- triazine, reaction temperature used in reaction process and reaction time are identical.Final product 5'- (3- (4,6- diphenyl -1,3 is formed under Pd (II) catalytic action by Hartwig reaction, 5- triazine -2-yl) phenyl) two spiral shell [fluorenes -9 of -5'H-, 7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes].MS (ASAP)=876.5.

Embodiment 5

Two spiral shell of 5'- (2- (4,6- diphenyl -1,3,5- triazine -2-yl) phenyl) -5'H- [fluorenes -9,7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes]

In the present embodiment, final product 5'- (2- (4, 6- diphenyl -1, 3, 5- triazine -2-yl) phenyl) two spiral shell [fluorenes -9 of -5'H-, 7'- naphtho- [2, 3-b] carbazole -12', 9 "-fluorenes] with embodiment 4 in product 5'- (3- (4, 6- diphenyl -1, 3, 5- triazine -2-yl) phenyl) two spiral shell [fluorenes -9 of -5'H-, 7'- naphtho- [2, 3-b] carbazole -12', 9 "-fluorenes] synthesis step it is similar, except that intermediate is by 2- (3- bromophenyl) -4, 6- diphenyl -1, 3, 5- triazine is replaced with 2- (2- bromophenyl) -4, 6- diphenyl -1, 3, 5- triazine, reaction temperature used in reaction process and reaction time are identical.Final product 5'- (2- (4,6- diphenyl -1,3 is formed under Pd (II) catalytic action by Hartwig reaction, 5- triazine -2-yl) phenyl) two spiral shell [fluorenes -9 of -5'H-, 7'- naphtho- [2,3-b] carbazole -12', 9 "-fluorenes] (5).MS (ASAP)=876.4.

The energy level of organic compound material can be calculated by quantum, for example using TD-DFT (time-depentent DFT) by Gaussian09W (Gaussian Inc.), specific analogy method can be found in WO2011141110.Semi-empirical approach " Ground State/Semi-empirical/Default Spin/AM1 " (Charge 0/Spin Singlet) Lai Youhua molecular geometry is used first, and then the energy-structure of organic molecule calculates " TD-SCF/DFT/Default Spin/B3PW91 " and base group " 6-31G (d) " (Charge 0/Spin Singlet) by TD-DFT (time-depentent DFT) method.HOMO and LUMO Energy level is calculated according to following calibration equation, S₁, T₁With resonance coefficient f (S₁) directly use.

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

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

Wherein HOMO (G) and LUMO (G) is the direct calculated result of Gaussian 09W, unit Hartree, as a result as shown in Table 1.

Table one

Material	HOMO[eV]	LUMO[eV]	f(S₁)	T₁[eV]	S₁[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

Wherein, resonance coefficient f (S₁) be between 0.001 to 0.119, the fluorescent quantum luminous efficiency of material can be improved well.And Δ E (S₁–T₁) value be not more than 0.20eV, meet be less than 0.30eV delayed fluorescence luminescent condition.

With above-mentioned prolong that fluorescence luminescent material is compared is the delayed fluorescence luminescent material of D-A architecture with the label of Ref 1:

The preparation of OLED device:

With ITO/NPD (35nm)/5% (1)~(5): DPEPO (15nm)/TPBi (65nm)/LiF (1nm)/Al (150nm)/cathode OLED device preparation step is as follows:

A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropanol are cleaned, and then carry out UV ozone plasma treatment；

B, HTL (35nm), EML (15nm), ETL (65nm): in high vacuum (1 × 10^-6Millibar, mbar) in hot evaporation form；

C, cathode: LiF/Al (1nm/150nm) is in high vacuum (1 × 10^-6Millibar) in hot evaporation form；

D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.

Current Voltage (J-V) characteristic of each OLED device is characterized by characterization equipment, while recording important parameter such as efficiency, service life and external quantum efficiency.Through detecting, the luminous efficiency of OLED1 (corresponding raw material (1)) and service life are all the 2 times or more of OLED Ref1 (corresponding raw material (Ref1)), the luminous efficiency of OLED3 (corresponding raw material (3)) is 3 times of OLED Ref1, and the service life is 4 times or more, the maximum external quantum efficiency of especially OLED3 reaches 10% or more.As it can be seen that the OLED device prepared using organic mixture of the invention, luminous efficiency and service life are greatly enhanced, and external quantum efficiency is also improved significantly.

Claims

A kind of organic compound for organic electronic device, which is characterized in that shown in the structure of the organic compound such as general formula (1):

Wherein,

Ar¹Selected from aromatic series, heteroaromatic or non-aromatic ring system with 5-20 carbon atom；Ar²It is not present or Ar²Aromatic series, heteroaromatic or non-aromatic ring system with 5-60 carbon atom；Ar¹Ring on all have group R¹；Work as Ar²Selected from aromatic series, heteroaromatic or when non-aromatic ring system with 5-60 carbon atom, Ar²Ring on all have group R¹；

X is selected from N or CR², and adjacent X is not all N；Y₁And Y₂Independently selected from C, Si or Ge；Z is selected from two bridges or three bridging bases, and Z and Ar¹Or Ar²It is connected with singly-bound or double bond；

R¹Selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR³)₂、Si(R³)₃, linear paraffin, alkane ether, containing 1~10 carbon atom alkane thioether, branched paraffin, cycloalkane or alkane ether group containing 3~10 carbon atoms；

R³Selected from H, D, the aliphatic alkane containing 1~10 carbon atom, aromatic hydrocarbon or containing 5~10 annular atoms take unsubstituted aromatic rings or heterocyclic base group；

R²Selected from H, D, straight chained alkyl with 1 to 20 C atom, alkoxy with 1 to 20 C atom, thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl with 3 to 20 C atoms, branch or cricoid alkoxy with 3 to 20 C atoms, branch or cricoid thio alkoxy group with 3 to 20 C atoms, silyl-group, substituted keto group with 1 to 20 C atom, alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF₃One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of.
Organic compound according to claim 1, which is characterized in that the Δ E (S of the organic compound₁-T₁)≤0.30eV；Wherein, Δ E (S₁-T₁) indicate the first triplet excited state T of the organic compound₁With its first singlet excited S₁Between energy level difference.
According to organic compound described in right 1, which is characterized in that the Z is selected from following any three abutment:

Wherein, R₄、R₅With R₆Independently selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR³)₂、Si(R³)₃, linear paraffin, alkane ether, containing 1~10 carbon atom alkane thioether, branched paraffin, cycloalkane or alkane ether group containing 3~10 carbon atoms；Dotted line key indicates any three abutment and structural unit Ar¹、Ar²Or the key of the C bonding on phenyl ring.
Organic compound according to claim 1, which is characterized in that the Y₁And Y₂At least one of be C.
Organic compound according to claim 1, which is characterized in that the Ar¹Selected from following any group:

Wherein, X₁Selected from CR⁷Or N；Y is selected from CR⁸R⁹、SiR¹⁰R¹¹、NR¹², C (=O), S or O；

R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²Independently selected from H, D, the straight chained alkyl with 1 to 20 C atom, the alkoxy with 1 to 20 C atom, the thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl, branch or cricoid alkoxy, branch or cricoid thio alkoxy group, branch or cricoid monosilane with 3 to 20 C atoms with 3 to 20 C atoms with 3 to 20 C atoms with 3 to 20 C atoms Base group, the substituted keto group with 1 to 20 C atom, the alkoxycarbonyl groups with 2 to 20 C atoms, the aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF₃One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system, the aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of；R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²In at least one ring for being bonded with the building stone form monocycle or polycyclic aliphatic series or aromatic ring or R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²In at least two be mutually bonded to form monocycle or polycyclic aliphatic series or aromatic ring.
Organic compound according to claim 1, which is characterized in that the Ar²Selected from following any group:

Wherein, 1,2,3 or 4 n.
Organic compound according to claim 1, which is characterized in that the Ar²Include electron-donating group or electron-withdrawing group.
Organic compound according to claim 7, which is characterized in that the electron-donating group is selected from following any group:
Organic compound according to claim 7, which is characterized in that the electron-withdrawing group is selected from F, cyano or following any group:

Wherein, 1,2 or 3 n；X¹-X⁸Independently selected from CR¹³Or N, and X¹-X⁸In at least one be N；R¹³Selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl.
Organic compound according to claim 1 to 9, which is characterized in that the organic compound is selected from one of the compound as described in flowering structure:
Application of the organic compound according to claim 1 to 10 in organic electronic device.
A kind of polymer, which is characterized in that at least one repetitive unit includes such as organic compound of any of claims 1-10 in the polymer.
A kind of organic mixture for organic electronic device, which is characterized in that the organic mixture includes at least one organic functional material and such as organic compound of any of claims 1-10；The organic functional material is selected from hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electron transport material, electron-blocking materials, organic host material or luminescent material.
A kind of composition, which is characterized in that the composition includes organic solvent and such as organic compound of any of claims 1-10 or polymer as claimed in claim 12.
A kind of organic electronic device, it is characterized in that, the organic electronic device includes functional layer, the functional layer includes that perhaps organic mixture as claimed in claim 13 or the functional layer are prepared by composition as claimed in claim 14 for such as organic compound of any of claims 1-10 or polymer as claimed in claim 12.
Organic electronic device according to claim 15, it is characterized in that, the organic electronic device is selected from Organic Light Emitting Diode, organic photovoltaic battery, organic light emission battery, organic field-effect tube, organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode.
Organic electronic device according to claim 16, which is characterized in that the organic electronic device is Organic Light Emitting Diode, and the organic electronic device includes luminescent layer, and the luminescent layer includes the organic compound or the polymer.