CN114262339B

CN114262339B - Organic compounds, mixtures, compositions and organic electronic devices containing boron heterocycles

Info

Publication number: CN114262339B
Application number: CN202010973038.2A
Authority: CN
Inventors: 宋鑫龙; 何锐锋; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2020-09-16
Filing date: 2020-09-16
Publication date: 2024-09-17
Anticipated expiration: 2040-09-16
Also published as: CN114262339A

Abstract

The present invention relates to organic compounds, mixtures, compositions and organic electronic devices containing boron heterocycles. The organic compound containing boron heterocycle has a structure shown in a formula (1), and can be used in luminescent material organic electronic devices to improve electroluminescent efficiency and prolong the service life of the devices.

Description

Organic compounds, mixtures, compositions and organic electronic devices containing boron heterocycles

Technical Field

The invention relates to the field of electroluminescent materials, in particular to a boron-heterocycle-containing organic compound, a mixture, a composition and an organic electronic device.

Background

Organic semiconductor materials have great potential for use in optoelectronic devices, particularly OLED devices, due to their synthetic versatility, relatively low manufacturing costs, and excellent optical and electrical properties.

Various luminescent material systems based on fluorescence and phosphorescence have been developed in order to improve the luminous efficiency of the organic light emitting diode, and the organic light emitting diode using the fluorescent material has a characteristic of high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3. In contrast, organic light emitting diodes using phosphorescent materials have achieved almost 100% internal electroluminescent quantum efficiency. However, phosphorescent OLEDs have a significant problem in that the Roll-off effect, i.e. the luminous efficiency decreases rapidly with increasing current or brightness, is particularly disadvantageous for high-brightness applications.

The phosphorescent materials which have been practically used up to now are iridium and platinum complexes, but the raw materials for preparing these compounds are rare and expensive, and the synthesis of the complexes is also complicated, and thus the cost is quite high. In order to overcome the problems of rare and expensive raw materials of iridium and platinum complexes and complex synthesis thereof, adachi proposed the concept of reverse internal conversion, so that high efficiency comparable to phosphorescent OLEDs can be achieved using organic compounds, i.e. without using metal complexes. This concept has been achieved by various combinations of materials, such as: 1) Using composite excited state materials (explex), see Adachi et al, nature Photonics, vol 6, p253 (2012); 2) Thermally excited delayed fluorescence (TADF) materials are utilized, see Adachi et al, nature, vol 492,234, (2012). However, the existing organic compounds with TADF mostly adopt a mode of connecting electron donating (Donor) groups with electron withdrawing (Acceptor) groups, so that the electron cloud distribution of the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO) is completely separated, and the difference (Δe _ST) between the singlet state (S ₁) and the triplet state (T ₁) of the organic compound is reduced.

The development of the existing red light and green light TADF materials has achieved a certain result in a plurality of performances, but compared with phosphorescent luminescent materials, the performances of the materials have a certain difference in efficiency and service life. Therefore, there is an urgent need to develop TADF materials that are efficient, long-lived, and inexpensive to manufacture.

Disclosure of Invention

In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a boron-containing heterocyclic organic compound and application thereof, and aims to provide a novel organic photoelectric functional material, which improves the efficiency and lifetime of the device and reduces the manufacturing cost.

The technical scheme of the invention is as follows:

A boron-containing heterocyclic organic compound has a structural general formula shown in a formula (1): wherein:

B is boron atom;

x is independently selected from B, N, P, as or Bi at each occurrence;

-represents a single bond or is absent;

Ar ₁-Ar₄ is independently selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 40 ring atoms, substituted or unsubstituted heteroaryl groups having from 5 to 40 ring atoms, and substituted or unsubstituted non-aromatic ring systems having from 5 to 40 ring atoms;

r ₁ is independently selected from the group consisting of, for each occurrence, hydrogen, deuterium, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl or cycloalkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, amine, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF ₃, cl, br, F, a crosslinkable group, a substituted or unsubstituted aryl having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, an aryloxy having 5 to 60 ring atoms, a heteroaryl having 5 to 60 ring atoms, or a combination of these.

The invention also provides a mixture, which comprises the organic compound containing the boron heterocycle and at least one organic functional material, wherein the organic functional material is at least one selected from hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials and organic dyes.

The invention also provides a composition comprising an organic compound containing a boron heterocycle as described above or a mixture of the above, and at least one organic solvent.

The invention also provides an organic electronic device, and the preparation raw materials of the electronic device at least comprise one boron-containing heterocyclic organic compound, or a mixture or a composition of the organic compound and the mixture.

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

the organic compound containing boron heterocycle provided by the invention is convenient for realizing the characteristic of thermal excitation delayed fluorescence luminescence (TADF) in a non-D-A structure, can be used as a luminescent material in an organic electronic device, can effectively improve the luminous efficiency and service life of the organic compound, and can be used as a solution of a luminescent device with low manufacturing cost, high efficiency, long service life and low roll-off.

Detailed Description

The invention provides a boron-containing heterocyclic organic compound, a mixture, a composition and application thereof. The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

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

In the present invention, the Host material, matrix material, host or Matrix material have the same meaning, and they are interchangeable with each other.

In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.

In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. If the general formula contains a plurality of R ₁、R₄, R ₁、R₄ can be independently selected from different groups.

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c _1-30 alkyl, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and which may be further substituted with art acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C _1-6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms, or heteroaryl containing 5 to 10 ring atoms; the C _1-6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms, or heteroaryl containing 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c _1-6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, for example, "C _1-9 alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, which at each occurrence may be, independently of one another, C ₁ alkyl, C ₂ alkyl, C ₃ alkyl, C ₄ alkyl, C ₅ alkyl, C ₆ alkyl, C ₇ alkyl, C ₈ alkyl or C ₉ alkyl. non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyl eicosanyl, 2-butyl eicosanyl, 2-hexyl eicosanyl, 2-octyl eicosanyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantane, and the like.

The term "alkoxy" refers to a group having an-O-alkyl group, i.e. an alkyl group as defined above, attached to the parent core structure via an oxygen atom. Phrases containing this term, suitable examples include, but are not limited to: methoxy (-O-CH 3 or-OMe), ethoxy (-O-CH 2CH3 or-OEt), and t-butoxy (-O-C (CH 3) 3 or-OtBu).

"Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic species. For example, "substituted or unsubstituted aryl having 5 to 60 ring atoms" refers to an aryl group containing 5 to 60 ring atoms, and the aryl group is optionally further substituted thereon; suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene, and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.

"Heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. For example, "substituted or unsubstituted heteroaryl having 5 to 60 ring atoms" refers to heteroaryl having 5 to 60 ring atoms, and heteroaryl is optionally further substituted, suitable examples include, but are not limited to: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, and quinazolinone.

In the present invention, m-membered aryl means aryl having m ring atoms, and m-membered heteroaryl means heteroaryl having m ring atoms, for example: "5-10 membered aryl" refers to aryl groups containing 5-10 ring atoms, and "5-10 membered heteroaryl" refers to heteroaryl groups containing 5-10 ring atoms.

"Amine group" refers to a derivative of ammonia having the structural features of formula-N (X) ₂, wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH ₂, -N (alkyl) ₂, -NH (alkyl), -N (cycloalkyl) ₂ -NH (cycloalkyl), -N (heterocyclyl) ₂, -NH (heterocyclyl), -N (aryl) ₂ -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.

"Halogen" or "halo" refers to F, cl, br or I.

"Alkylamino" refers to an amino group substituted with at least one alkyl group. Suitable examples include, but are not limited to ：-NH₂、-NH(CH₃)、-N(CH₃)₂、-NH(CH₂CH₃)、-N(CH₂CH₃)₂.

"Arylalkyl" refers to a hydrocarbon radical derived from an alkyl group in which at least one hydrogen atom bonded to a carbon atom is replaced with an aryl group. Wherein the aryl moiety may comprise from 5 to 20 carbon atoms and the alkyl moiety may comprise from 1 to 9 carbon atoms. Suitable examples include, but are not limited to: benzyl, 2-phenylethan-1-yl, naphthylmethyl, 2-naphthylethan-1-yl, naphthobenzyl and 2-naphthophenylethan-1-yl.

In the present invention "×" attached to a single bond represents the attachment site; in the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR ₂ in (B) is attached to any substitutable position of the benzene ring, e.gRepresentation ofY ₁ and Y ₂ form a fused ring with optionally two adjacent C atoms of the benzene ring, and so onEtc.

In the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for exampleThe 6R ¹ groups on the benzene ring may be the same or different from each other.

In the present invention, the abbreviations of the substituents correspond to: n-n, sec-sec, i-iso, t-tert, o-o, m-m, p-pair, memethyl, et ethyl, pr propyl, bu butyl, am-n-pentyl, hx hexyl, cy cyclohexyl.

In the embodiment of the invention, the energy level structure of the organic material and triplet energy levels E _T, HOMO and LUMO play a key role. These energy levels are described below.

HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level E _T1 of the organic material can be measured by low temperature Time resolved luminescence spectroscopy or obtained by quantum simulation calculations (e.g. by Time-DEPENDENT DFT), such as by commercial software Gaussian 03W (Gaussian inc.) for specific simulation methods see WO2011141110 or as described in the examples below.

It should be noted that the absolute value of HOMO, LUMO, E _T1 depends on the measurement or calculation method used, and even for the same method, different evaluation methods, e.g. starting points and peak points on the CV curve, may give different HOMO/LUMO values. Thus, a reasonable and meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the value HOMO, LUMO, E _T1 is based on a simulation of Time-DEPENDENT DFT, but does not affect the application of other measurement or calculation methods.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (lumo+1) is defined as the second lowest unoccupied orbital level, (lumo+2) is the third lowest occupied orbital level, and so on.

The invention provides a boron-containing heterocyclic organic compound, which has a structural general formula shown in a formula (1):

B is boron atom;

x is independently selected from B, N, P, as or Bi at each occurrence;

-represents a single bond or is absent;

In the present invention, the substitution means substitution with R, and R has the same meaning as R ₁.

In one embodiment, X is selected from N or P. Preferably, X is selected from N.

In one embodiment, the organic compound has a general structural formula selected from any one of formulas (2-1) - (2-3):

Ar ₁-Ar₄ is independently selected from any one structure of (A-1) - (A-6):

Wherein:

Each occurrence of X ₁ is independently selected from CR ₂ or N; preferably, each occurrence of said X ₁ is independently selected from CR ₂;

Y ₁ is independently selected from NR₃、CR₃R₄、SiR₃R₄、O、CO、C＝NR₃、C＝C(R₃R₄)、PR₃、P(＝O)R₃、S、S＝O or SO ₂;

y ₂ is independently selected from single bond 、NR₃、CR₃R₄、SiR₃R₄、O、CO、C＝NR₃、C＝C(R₃R₄)、PR₃、P(＝O)R₃、S、S＝O or SO ₂;

each occurrence of R ₂、R₃、R₄ is independently selected from: hydrogen, deuterium, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl or cycloalkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, amine, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF ₃, cl, br, F, crosslinkable groups, substituted or unsubstituted aryl having 5 to 60 ring atoms, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, aryloxy having 5 to 60 ring atoms, heteroaryloxy having 5 to 60 ring atoms, or a combination of these groups.

When X ₁ is a ligation site, X ₁ is selected from C.

In one embodiment, ar ₁ is selected from (A-1), (A-2) (A-3), (A-4), or (A-6); ar ₃ is selected from (A-2), (A-3), (A-4), (A-5) or (A-6).

In one embodiment, ar ₁-Ar₄ is selected from (A-2). The structural general formula of the organic compound is selected from the formula (3-1):

In one embodiment Ar ₁ is selected from (A-1), (A-3), (A-4) or (A-6).

In one embodiment, ar ₃ is selected from (A-1), (A-3), (A-4), or (A-6).

In one embodiment, at least one of Ar ₁-Ar₄ is selected from (A-4), (A-5), or (A-6).

In one embodiment, at least two of Ar ₁-Ar₄ are selected from (A-4), (A-5) or (A-6); further, ar ₁ and Ar ₂ are selected from (A-4), (A-5) or (A-6), or Ar ₃ and Ar ₄ are selected from (A-4), (A-5) or (A-6).

In one embodiment, the organic compound has a structure selected from any one of formulas (3-2) - (3-7):

in one embodiment, Y ₂ is selected from single bonds.

In one embodiment, at least one of Ar ₁-Ar₄ is selected from (A-1) or (A-3).

In one embodiment, at least two of Ar ₁-Ar₄ are selected from (A-1) or (A-3), further Ar ₁ and Ar ₂ are selected from (A-1) or (A-3), or Ar ₃ and Ar ₄ are selected from (A-1) or (A-3).

Preferably, the structural general formula of the organic compound is selected from any one of formulas (3-8) - (3-11):

Further, each occurrence of X ₁ is selected from CR ₂.

Preferably, the structural general formula of the organic compound is selected from any one of formulas (4-1) to (4-12):

Wherein:

a. b, c and d are independently selected from any integer from 0 to 3.

In one embodiment, a+b+c+d is greater than or equal to 1; in one embodiment, a+b+c+d is greater than or equal to 2; in one embodiment, a+b+c+d is 3; in one embodiment, a+b+c+d is greater than or equal to 4; in one embodiment, a+b+c+d is greater than or equal to 5; in one embodiment, a+b+c+d is ≡6.

In one embodiment, a, b are independently selected from any integer from 1-3;

in one embodiment, c, d are independently selected from any integer from 1-3;

in one embodiment a, b, c, d is independently selected from any integer from 1-3.

In one embodiment, R ₁、R₂、R₃ and R ₄ are each independently selected from hydrogen, straight chain alkyl having 1 to 10C atoms, branched alkyl having 3 to 10C atoms, amine, or heteroaromatic having 5 to 30 ring atoms or 5 to 30 ring atoms substituted with 1 to 10C atoms, or heteroaromatic having 5 to 30 ring atoms substituted with 1-10C atoms.

In one embodiment, at least one of R ₁、R₂、R₃ and R ₄ is selected from a linear alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, an amine group, or a heteroaromatic group having 5 to 30 ring atoms or 5 to 30 ring atoms substituted with 1 to 10C atoms, or a heteroaromatic group having 5 to 30 ring atoms substituted with 1-10C atoms.

Further, R ₁、R₂、R₃ and R ₄ are each independently selected from hydrogen, a straight chain alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, or a group A1; preferably, at least one of R ₁、R₂、R₃ and R ₄ is selected from a linear alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, or a group A1;

the group A1 group includes the following groups:

Each occurrence of X ₂ is independently selected from: CR ₅ or N;

Y ₃ is a single bond, CR ₆R₇、O、S、SO₂ or NR ₆;

Each occurrence of said R ₅、R₆ and R ₇ is independently selected from the group consisting of: hydrogen, deuterium, straight chain alkyl having 1 to 20C atoms, branched alkyl or cycloalkyl having 3 to 20C atoms, silyl, substituted or unsubstituted aryl having 5 to 30 ring atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring atoms.

Further, each occurrence of R ₅ is independently selected from: hydrogen or methyl orN is 0,1,2, 3 or 4.

In one embodiment, at least one of R ₁、R₂ and R ₅ comprises a methyl group orAnd n is 0, 1, 2, 3 or 4.

In one embodiment, R ₁、R₂ and R ₅ are independently selected from hydrogen, methyl, tBu, tAm, or the following; further, at least one R ₄ is selected from: methyl, tBu, tmam or the following groups;

Wherein:

Each occurrence of R ₈ is independently selected from: deuterium, a straight chain alkyl group having 1 to 10C atoms, a branched alkyl or cycloalkyl group having 3 to 10C atoms, a silyl group, a substituted or unsubstituted aryl group having 5 to 10 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 15 ring atoms.

E is selected from 0, 1,2, 3 or 4; f is selected from 0, 1,2 or 3; g is selected from 0, 1,2, 3, 4 or 5.

Preferably, R ₈ is independently selected at each occurrence from methyl or

A is selected from 0, 1,2, 3 or 4; b is selected from 0, 1,2 or 3; c is selected from 0, 1,2, 3, 4 or 5.

TAm represents 2- (2-methyl) butyl; tBu represents tert-butyl.

Examples of organic compounds according to the present invention are listed below, but are not limited to:

the compound according to the invention can be used as a functional material in electronic devices, in particular OLED devices. The organic functional layer includes, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitter (Emitter), a Host material (Host), and an organic dye.

In one embodiment, the organic compound according to the present invention may be used in a light emitting layer, and preferably, may be used in a light emitting layer as a guest material of a light emitting layer; further, it can be used as blue light guest material in the light emitting layer.

The invention also relates to a mixture comprising an organic compound as described above and at least one organic functional material. The organic functional material comprises a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting body or a main body material. The luminophore is selected from singlet luminophore (fluorescent luminophore), triplet luminophore (phosphorescent luminophore) class organic thermal excitation delayed fluorescence material (TADF material). Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference. The organic functional material may be small molecule and high polymer materials.

In an embodiment, the another organic functional material is selected from a host material; further, the another organic functional material is selected from blue host materials.

The present invention also provides a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, borate or phosphate compound, or mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention, said at least one organic solvent is chosen from solvents based on aromatic or heteroaromatic groups.

Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;

Examples of aromatic ketone-based solvents suitable for the present invention are, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;

Examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, 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-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

In some preferred embodiments, the composition according to the invention, said at least one solvent may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl 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, and the like.

In other preferred embodiments, the at least one solvent according to the compositions of the present invention may be chosen from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate.

The solvent may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are solvents having Hansen (Hansen) solubility parameters within the following ranges:

δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;

δp (polar force) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2;

δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2.

The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; and most preferably at a temperature of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a film comprising the functional material.

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

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

The compositions according to embodiments of the present invention may comprise from 0.01% to 10% by weight of a compound or mixture according to the present invention, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 5% by weight, most preferably from 0.25% to 3% by weight.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by printing or coating.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. The printing technology and the related requirements of the solution, such as solvent, concentration, viscosity and the like.

The invention also provides the use of an organic compound, mixture or composition as described above in an organic electronic device selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (olecs), organic Field Effect Transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors, organic plasmon emitting diodes (Organic Plasmon Emitting Diode) and the like, particularly preferably OLEDs. In the embodiment of the invention, the organic compound is preferably used for a light emitting layer of an OLED device.

The present invention provides a functional layer comprising the above-mentioned organic compound.

Further, the functional layer is a light-emitting layer, the light-emitting layer comprises a host material and a guest material, and the guest material is the organic compound; further, the mass ratio of the host material to the guest material is (8-12): 1, a step of; further, the mass ratio of host material to guest material is 10:1.

The invention further relates to an organic electronic device comprising at least one functional layer comprising an organic compound, mixture or prepared from the composition as described above. Further, the organic electronic device comprises a cathode, an anode and at least one functional layer comprising or being prepared from a polycyclic compound or mixture as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emitting layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL); preferably, the functional layer is selected from light emitting layers.

Further, the organic electronic device may be selected from, but not limited to, organic Light Emitting Diode (OLED), organic photovoltaic cell (OPV), organic light emitting cell (OLEEC), organic Field Effect Transistor (OFET), organic light emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and particularly preferred is an organic electroluminescent device such as OLED, OLEEC, organic light emitting field effect transistor.

In the light emitting device, especially the OLED, the light emitting device comprises a substrate, an anode, at least one light emitting layer and a cathode.

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

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials 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, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.

In a preferred embodiment, the light-emitting layer of the light-emitting device according to the invention is prepared from the composition according to the invention.

The light emitting device according to the present invention has a light emitting wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

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

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of Compounds

Example 1

The synthetic route for compound 1 is shown in the following figure:

(1) Synthesis of intermediate 1-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 1-1 and 1mmol of intermediate 1-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 1-3 with the molar quantity of 0.47mmol, wherein the reaction yield is as follows: 47%, MS (ASAP) =540.7.

(2) Synthesis of Compound (1):

To a 250mL three-necked flask, 10mmol of intermediate 1-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an N ₂ atmosphere, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 72.6%, MS (ASAP) =470.2.

Example 2

The synthetic route for compound 2 is shown in the following figure:

(1) Synthesis of intermediate 2-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 2-1 and 1mmol of intermediate 2-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 2-3 with the molar quantity of 0.85mmol, wherein the reaction yield is as follows: 85%, MS (ASAP) = 1038.6.

(2) Synthesis of Compound (2):

To a 250mL three-necked flask, 10mmol of intermediate 2-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an N ₂ atmosphere, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 63.5%, MS (ASAP) = 968.2.

Example 3

The synthetic route for compound 3 is shown in the following figure:

(1) Synthesis of intermediate 3-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 3-1 and 1mmol of intermediate 3-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 3-3 with the molar quantity of 0.75mmol, wherein the reaction yield is as follows: 75%, MS (ASAP) = 1306.7.

Synthesis of compound (3):

To a 250mL three-necked flask, 10mmol of intermediate 3-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an N ₂ atmosphere, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 47.6%, MS (ASAP) = 1236.5.

Example 4

The synthetic route for compound 4 is shown in the following figure:

(1) Synthesis of intermediate 4-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 4-1 and 1mmol of intermediate 4-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 4-3 with the molar quantity of 0.67mmol, wherein the reaction yield is as follows: 67%, MS (ASAP) = 1038.1.

Synthesis of Compound (4):

To a 250mL three-necked flask, 10mmol of intermediate 4-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an atmosphere of N ₂, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield was 51.2%, MS (ASAP) = 968.7.

Example 5

The synthetic route for compound 5 is shown in the following figure:

(1) Synthesis of intermediate 5-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 5-1 and 1mmol of intermediate 5-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 5-3 with the molar quantity of 0.73mmol, wherein the reaction yield is as follows: 73%, MS (ASAP) = 684.3.

Synthesis of compound (5):

To a 250mL three-necked flask, 10mmol of intermediate 5-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an atmosphere of N ₂, and a 30.6mmol t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield was 37.4%, MS (ASAP) = 614.9.

Example 6

The synthetic route for compound 6 is shown in the following figure:

(1) Synthesis of intermediate 6-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 6-1 and 1mmol of intermediate 6-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 6-3 with the molar quantity of 0.76mmol, wherein the reaction yield is as follows: 76, MS (ASAP) = 664.2.

Synthesis of Compound (6):

To a 250mL three-necked flask, 10mmol of intermediate 6-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an N ₂ atmosphere, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 43.9%, MS (ASAP) = 594.3.

Example 7

The synthetic route for compound 7 is shown in the following figure:

(1) Synthesis of intermediate 7-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 7-1 and 1mmol of intermediate 7-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 7-3 with the molar quantity of 0.82mmol, wherein the reaction yield is as follows: 82%, MS (ASAP) = 914.6.

Synthesis of compound (7):

To a 250mL three-necked flask, 10mmol of intermediate 7-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an N ₂ atmosphere, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 57.3%, MS (ASAP) = 844.2.

Example 8

The synthetic route for compound 8 is shown in the following figure:

(1) Synthesis of intermediate 8-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 8-1 and 1mmol of intermediate 8-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 8-3 with the molar quantity of 0.74mmol, wherein the reaction yield is as follows: 74%, MS (ASAP) = 726.8.

Synthesis of Compound (8):

To a 250mL three-necked flask, 10mmol of intermediate 8-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an atmosphere of N ₂, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 38.9%, MS (ASAP) =656.3.

Example 9

The synthetic route for compound 9 is shown in the following figure:

(1) Synthesis of intermediate 9-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 9-1 and 1mmol of intermediate 9-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, simultaneously extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 9-3 with the molar weight of 0.62mmol, wherein the reaction yield is as follows: 62%, MS (ASAP) = 672.3.

Synthesis of compound (9):

To a 250mL three-necked flask, 10mmol of intermediate 9-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an atmosphere of N ₂, and a 30.6mmol t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 41.6%, MS (ASAP) =602.4.

Example 10

The synthetic route for compound 10 is shown in the following figure:

(1) Synthesis of intermediate 10-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 10-1 and 1mmol of intermediate 10-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, simultaneously extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 10-3 with the molar weight of 0.54mmol, wherein the reaction yield is as follows: 54%, MS (ASAP) = 738.6.

Synthesis of compound (10):

To a 250mL three-necked flask, 10mmol of intermediate 10-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃in an atmosphere of N ₂, followed by dropwise addition of a 30.6mmol t-BuLi N-hexane solution. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 74.3%, MS (ASAP) = 668.2.

Example 11

The synthetic route for compound 11 is shown in the following figure:

(1) Synthesis of intermediate 11-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 11-1 and 1mmol of intermediate 11-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 11-3 with the molar quantity of 0.69mmol, wherein the reaction yield is as follows: 69%, MS (ASAP) = 866.3.

Synthesis of Compound (11):

Into a 250mL three-necked flask, 10mmol of the intermediate 11-3 and 100mL of dry tert-butylbenzene were charged, and the mixture was cooled to-30℃in an atmosphere of N ₂, and a 30.6mmol of t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 63.2%, MS (ASAP) = 796.5.

Example 12

The synthetic route for compound 12 is shown in the following figure:

(1) Synthesis of intermediate 12-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 12-1 and 1mmol of intermediate 12-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 12-3 with the molar quantity of 0.57mmol, wherein the reaction yield is as follows: 57%, MS (ASAP) = 742.6.

Synthesis of compound (12):

Into a 250mL three-necked flask, 10mmol of the intermediate 12-3 and 100mL of dry tert-butylbenzene were charged, and the mixture was cooled to-30℃under an atmosphere of N ₂, and a 30.6mmol of t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 45.6%, MS (ASAP) = 672.9.

Example 13

The synthetic route for compound 13 is shown in the following figure:

(1) Synthesis of intermediate 13-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 13-1 and 1mmol of intermediate 13-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 13-3 with the molar quantity of 0.69mmol, wherein the reaction yield is as follows: 69%, MS (ASAP) =474.1.

Synthesis of Compound (13):

Into a 250mL three-necked flask, 10mmol of intermediate 13-3 and 100mL of dry tert-butylbenzene were added, and the mixture was cooled to-30℃under an atmosphere of N ₂, and a 30.6mmol of t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield was 63.3%, MS (ASAP) =404.7.

Example 14

The synthetic route for compound 14 is shown in the following figure:

(1) Synthesis of intermediate 14-3:

In a dry three-neck flask under the protection of nitrogen, respectively adding 1mmol of intermediate 14-1 and 1mmol of intermediate 14-2, pouring 100mL of DMSO as a solvent, adding dry K ₂CO₃ as alkali, reacting for 8 hours at 120 ℃, monitoring the reaction by TLC, cooling the reaction liquid to room temperature after the reaction is completed, sequentially adding water and dichloromethane, washing the reaction liquid for multiple times by using the water, extracting the water phase for multiple times by using the dichloromethane, merging the organic phases, drying by using anhydrous Na ₂CO₃, filtering, spinning the reaction liquid to obtain a crude product, and recrystallizing by using ethyl acetate to obtain the intermediate 14-3 with the molar quantity of 0.87mmol, wherein the reaction yield is as follows: 87%, MS (ASAP) =484.2

Synthesis of Compound (14):

Into a 250mL three-necked flask, 10mmol of intermediate 14-3 and 100mL of dry tert-butylbenzene were charged, and the mixture was cooled to-30℃in an atmosphere of N ₂, and a 30.6mmol of t-BuLi N-hexane solution was added dropwise. The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30℃and 10.5mol of boron tribromide solution was added and stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0℃and 21mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, the temperature was raised to room temperature and stirred, and then the temperature was raised to 120℃again and stirred for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted by ethyl acetate, the organic phases are combined, the solvent in the aqueous phase is removed by rotary evaporation, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystallizing with toluene and ethyl acetate to obtain yellowish solid powder. Yield 74.3%, MS (ASAP) =554.1.

2. Preparation and characterization of OLED devices

The energy level of the organic compound material can be obtained by quantum computation, for example by means of a Gaussian09W (Gaussian inc.) using a TD-DFT (time-dependent density functional theory), and a specific simulation method can be seen in WO2011141110. The molecular geometry is first optimized by the Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/SPIN SINGLET), and then the energy structure of the organic molecule is calculated by the TD-DFT (time-Density functional theory) method to "TD-SCF/DFT/Default Spin/B3PW91" and the basis set "6-31G (d)" (Charge 0/SPIN SINGLET). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1, T1 and resonance factor f (S1) are directly used.

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

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

Wherein HOMO, LUMO, T1 and S1 are direct calculations of Gaussian 09W in Hartree. The results are shown in Table 1:

TABLE 1

The following describes in detail the preparation process of the OLED device using the above compound by specific examples, the OLED device having the structure: ITO/HIL/HTL/EML/ETL/cathode, the preparation steps are as follows:

a. Cleaning an ITO (indium tin oxide) conductive glass substrate: cleaning with various solvents (such as chloroform, acetone or isopropanol, or both), and performing ultraviolet ozone treatment;

b. HIL (hole injection layer, 40 nm) 60nm PEDOT (polyethylene dioxythiophene, clevelos ^TM AI 4083) as HIL was spin coated in an ultra clean room and treated on a hot plate at 180 ℃ for 10 minutes;

c. HTL (hole transport layer, 20 nm) of TFB or PVK (SIGMA ALDRICH, average Mn 25,000-50,000) at 20nm was spin-coated in a nitrogen glove box using a solution of TFB or PVK added to toluene solvent at a solution solubility of 5mg/mL followed by treatment on a hot plate at 180℃for 60 minutes;

d. EML (organic light-emitting layer, 40 nm) EML was prepared by spin coating in a nitrogen glove box using methyl benzoate solutions of different hosts (weight ratio of host to guest 95:5), solution solubility 15mg/mL, followed by treatment on a hot plate at 140℃for 10min, host structure BH, using the compounds synthesized in examples 1-15, all other embodiments being identical.

E. Electron transport layer and cathode transfer the heat treated substrate to a vacuum chamber, then place ET and Liq in different evaporation units, co-deposit them in a high vacuum (1 x 10-6 mbar) at a ratio of 50 wt% respectively, form an electron transport layer of 20nm on the light emitting layer, and then redeposit an Al cathode of 100nm thickness.

F. Encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.

The materials BH, ET, liq, BD-Ref are commercially available, or their synthesis methods are known in the art, and detailed references in the art are not described herein. Wherein BH is used as a main body material, ET is used as an electron transport material, and Liq is used as an electron injection material.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime and external quantum efficiency, the results are shown in table 2:

TABLE 2

As can be seen from table 2, the light emitting device containing the structural compound of the present invention has superior light emitting efficiency and service life compared to OLED-Ref.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. The organic compound containing boron heterocycle is characterized in that the structural general formula is shown as formula (4-1) or formula (4-10):

Wherein:

B is boron atom;

X is selected from N;

- - - - - - - - - - - - - - - - - - - - - - - - - - - - -, - - -means absence of;

each occurrence of R ₂ is independently selected from: hydrogen or a group of groups A1,

The group A1 group includes the following groups:

x ₂ is selected from CR ₅,Y₃ as a single bond;

Each occurrence of R ₅ is independently selected from: hydrogen or tert-butyl;

R ₁ is selected from hydrogen;

a. b, c and d are independently selected from any integer from 0 to 3.

2. A mixture comprising an organic compound comprising a boron-containing heterocycle as claimed in claim 1 and at least one organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting body, a host material and an organic dye.

3. A composition comprising a boron-containing heterocyclic organic compound according to claim 1 or a mixture according to claim 2, and at least one organic solvent.

4. An organic electronic device comprising at least one functional layer comprising the boron-containing heterocyclic organic compound of claim 1, or the mixture of claim 2, or prepared from the composition of claim 3;

The functional layer is one or more selected from a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, an electron injection layer, an electron transport layer and a hole blocking layer.