CN112851702A

CN112851702A - Organic boron compound, polymer, mixture and organic electronic device

Info

Publication number: CN112851702A
Application number: CN202110043052.7A
Authority: CN
Inventors: 廖良生; 蒋佐权; 郁友军
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2021-01-13
Filing date: 2021-01-13
Publication date: 2021-05-28
Anticipated expiration: 2041-01-13
Also published as: CN112851702B

Abstract

The present invention relates to an organoboron compound, a polymer, a mixture and an organic electronic device, wherein the organoboron compound comprises compounds represented by the following general formulae (1), (2), (3), (4), (5) and (6):

wherein Ar is¹～Ar⁵Having substituent groups R on the radical¹。Ar¹～Ar⁵Group, A¹～A⁵Group and R¹The radicals are defined in the description. The organic boron compound, the polymer and the mixture have excellent luminescence property and can be used as an organic luminescent deviceThe organic material layer, especially the core luminescent layer, realizes high efficiency and high color purity of the organic light emitting diode device.

Description

Organic boron compound, polymer, mixture and organic electronic device

Technical Field

The invention relates to the field of electroluminescence, in particular to organic boron compounds, polymers, mixtures and organic electronic devices.

Background

The organic light-emitting material has the characteristics of easiness in synthesis, easiness in derivation, excellent photoelectric property and the like, so that the organic light-emitting diode (OLED) has great application value and commercial potential in the fields of illumination, display and the like. Recently developed Thermally Activated Delayed Fluorescence (TADF) materials enable the utilization of both singlet excitons and triplet excitons in pure organic systems free of heavy metal elements. Currently, most TADF light emitting materials are composed of an electron donor (donor, D) and an electron acceptor (acceptor, a) connected by a single bond. The highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) electron clouds overlap to a lesser extent and the single triplet level difference is smaller. The spectrum of most TADF phosphors has a problem of a wide half-peak width due to a twisted structure.

Disclosure of Invention

An organic boron compound, the structure of which is shown in general formula (1), (2), (3), (4), (5) and (6):

wherein Ar is¹～Ar⁵The radicals are identical or different, Ar¹～Ar⁵Each independently selected from any one of aromatic, heteroaromatic or non-aromatic ring systems of 2-30 carbon atoms;

ar is¹～Ar⁵Having R on the ring of the radical¹Group R¹The groups are the same or different at each occurrence; the R is¹The group is selected from H, D, linear alkanes having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, thioalkoxy groups having 1 to 20 carbon atoms, branched chains having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, silyl groups having 3 to 20 carbon atoms, keto groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms, cyano groups, carbamoyl groups, haloformyl groups, formyl groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, substituted aryl groups, substituted,Nitro groups, ester groups, trifluoromethyl groups, Cl, Br, I, F, crosslinkable groups, substituted or unsubstituted aromatic or heteroaromatic ring systems containing from 5 to 40 ring atoms, having one or more substituted or unsubstituted aryloxy or heteroaryloxy groups containing from 5 to 40 ring atoms;

A¹～A⁵the radicals are identical or different, A¹～A⁵Each group is independently a single bond or a double bridge.

An organoboron polymer, at least one of the repeating units of which comprises the organoboron compound described above.

An organoboron mixture comprising the organoboron compound or the organoboron polymer and at least one organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, a light emitting material and a host material.

An organic electronic device comprising a light-emitting layer made of any one of the above-mentioned organoboron compound, organoboron polymer, or organoboron mixture.

The organic boron compound and the organic boron polymer adopt a plurality of bridge bonds to bond arylamine elements and organic boron elements, thereby greatly improving the molecular rigidity; meanwhile, the single triplet state energy gaps of the molecules are matched, so that the utilization of triplet state excitons can be realized, and the realization of electroluminescence with high color purity and high efficiency is facilitated. And the adjustment of the light-emitting wavelength from blue light to red light can be realized through the change of the conjugated unit and the bridge bond. Thereby facilitating application on the display.

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

Drawings

FIG. 1 is a general structural formula of an organoboron compound of the present invention;

FIG. 2 is a normalized electroluminescence spectrum of examples 47 and 48;

FIG. 3 is a schematic view of device structures of embodiments 47 to 53.

Wherein the content of the first and second substances,

1: substrate and positive electrode

2: hole injection layer

3: hole transport layer

4: electron blocking layer

5: luminescent layer

6: exciton blocking layer

7: electron transport layer

8: electron injection layer

9: negative electrode

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The organoboron compound of one embodiment has the structure shown in general formulas (1), (2), (3), (4), (5), and (6):

wherein Ar is¹～Ar⁵Identical or different, Ar¹～Ar⁵Independently selected from aromatic, heteroaromatic or non-aromatic ring systems of 2 to 30 carbon atoms; ar (Ar)¹～Ar⁵Having a group R on the ring¹Said R is¹The same or different at each occurrence.

A¹～A⁵Identical or different, independently selected from the group consisting of a single bond, a double bridge bond, A¹～A⁵Independently with its adjacent groups, by single or double bonds.

R¹Selected from H, D, linear alkanes having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, thioalkoxy groups having 1 to 20 carbon atoms, branches having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, silyl groups having 3 to 20 carbon atoms, keto groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms, cyano groups, carbamoyl groups, haloformyl groups, formyl groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, nitro groups, ester groups, trifluoromethyl groups, Cl, Br, I, F, crosslinkable groups, substituted or unsubstituted aromatic or heteroaromatic ring systems containing 5 to 40 ring atoms, having one or more substituted or unsubstituted aryloxy or heteroaryloxy groups containing 5 to 40 ring atoms.

In one embodiment, the compound according to the present invention, Ar¹～Ar⁵Each independently comprising at least one group of the structure:

wherein:

when X is plural in the same group, each X is independently selected from N or CR²。

When there are plural Y's in the same group, each Y is independently selected from CR³R⁴，SiR³R⁴，NR³，BR³，C(＝O)，S(＝O)，S(＝O)₂S or O; r²、R³、R⁴Is as defined for R¹。

In one embodiment, Ar¹～Ar⁵Each independently selected from the group consisting of:

wherein the dotted line represents a bond to an adjacent group.

In one embodiment, A¹～A⁵The same or different at each occurrence is a single bond or a double bridge.

In one embodiment, the said two bridges are selected from the following groups:

wherein Ar is⁶、Ar⁷With the above-mentioned Ar¹～Ar⁵The definitions are the same; the dotted line represents a bond to an adjacent group.

In one embodiment, A¹～A⁵Each independently selected from the group consisting of:

in one embodiment, the H atom on the NH or the bridging group CH in the organoboron compound₂Can be substituted by R₁And (4) substituting the group. R₁The group may be selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl or heteroaryl group having 2 to 10 carbon atoms. Wherein the alkyl group having 1 to 20 carbon atoms may be selected from methyl, ethyl, n-propylAlkyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2, 2, 2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. The alkoxy group having 1 to 10 carbon atoms may be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy. The aryl or heteroaryl radicals having from 2 to 20 carbon atoms may, depending on the use, be monovalent or divalent, and may in each case also be represented by the radicals R mentioned above₁Substituted and may be attached to the aromatic or heteroaromatic ring via any desired position. Further, the aryl or heteroaryl group having 2 to 20 carbon atoms may be selected from benzene, naphthalene, anthracene, perylene, dihydropyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroizole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, perylene, indole, fluoranthene, xanthene, dibenzofuran, thiophene, carbazole, pyridine, Benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazaanthracene, 1, 5-diazaanthracene, azocarbazole, benzocarbazine, phenanthroline, 1, 2, 3-triazole, 1, 2, 4-triazole, benzotriazole, 1, 2, 3-oxadiazole, 1, 2, 4-oxadiazole, 1, 2, 5-oxadiazole, 1, 2, 3-thiadiazole, 1, 2, 4-thiadiazole, 1, 2, 5-thiadiazole, 1, 3, 4-thiadiazole, 1, 3, 5-triazine, 1, 2, 4-triazine, 1, 2, 3-triazine, tetrazole, 1, 2, 4, 5-tetrazine, 1, 2,3, 5-tetrazine, 1, 2, 3, 4-tetrazine, purine, pteridine, indolizine or benzothiadiazole.

In a particularly preferred embodiment, Ar¹～Ar³Is phenyl. B is located para to the bridged triphenylamine group, and the compounds according to the present invention have one of the following general formulae:

wherein the symbol definitions are the same as above. In the general formula, the benzene ring has a group R¹Said R is¹The same or different at each occurrence.

In a more preferred embodiment, the organoboron compounds according to the invention are at least partially deuterated, preferably 10% H is deuterated, more preferably 20% H is deuterated, even more preferably 30% H is deuterated, and most preferably 40% H is deuterated.

The present invention also relates to an organoboron polymer whose repeating units contain the structure of the organoboron organic compound described above.

In certain embodiments, the organoboron polymer is a nonconjugated polymer. Containing a structural unit represented by the general formula (1) in a side chain. In other embodiments, the organoboron polymer is a conjugated polymer.

In a preferred embodiment, the organoboron polymers according to the invention have a molecular weight distribution (PDI) in the range from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2, most preferably from 1 to 1.5.

In a preferred embodiment, the organoboron polymers according to the invention have a weight average molecular weight in the range of from 1 to 100, preferably from 5 to 50, more preferably from 10 to 40, most preferably from 20 to 25, million.

The organic boron polymer can be applied to organic functional materials. The organoboron organic compounds described above can also be used in organic electronic devices.

The organic boron compound can be used as a functional material to be applied to organic electronic devices, in particular OLED devices. The organic functional material may be classified into a hole injection material, a hole transport material, an electron injection material, an electron transport material, an electron blocking material, a hole blocking material, a light emitting material, a host material, and an organic dye.

In a preferred embodiment, the organoboron compounds according to the invention can be used as light-emitting guest materials.

In some embodiments, the organoboron compounds according to the invention have a light-emitting function with a wavelength of between 300-780nm, preferably 400-680nm, more preferably 460-630 nm. Luminescence here refers to electroluminescence or photoluminescence. Further, the organoboron compound according to the present invention can be used as a light emitting material.

The following list is given of preferred organoboron compounds, but not limited thereto, all possible sites on these structures may be substituted.

In one embodiment, the organoboron compound according to the invention is a small molecule material. So that the organic boron compound of the invention is more suitable for evaporation type OLED. Wherein, in one embodiment, the organoboron compound of the invention has a molecular weight of 1500 g/mol or less. Further, the organoboron compound of the present invention has a molecular weight of 900 g/mol or less. Still further, the organoboron compound of the present invention has a molecular weight of 800 g/mol or less. Still further, the organoboron compound of the present invention has a molecular weight of 800 g/mol or less.

In one embodiment, the organoboron compound has a molecular weight of 700 g/mole or greater, making the organoboron compound more suitable for use in printed OLEDs. Further, the organoboron compound has a molecular weight of 800 g/mol or more. Further, the organoboron compound has a molecular weight of 900 g/mol or more. Further, the organoboron compound has a molecular weight of 1000 g/mole or more. Further, the organoboron compound has a molecular weight of 1500 g/mole or greater.

Based on the organoboron containing compound, the present invention also provides a use of the organoboron containing compound as described above, i.e., applying the organoboron containing compound to an organic electronic device, the organic electronic device comprising (but not limited to): organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), organic light emitting field effect transistors (efets), organic lasers, organic spintronic devices, organic sensors, and organic plasma-based light emitting diodes, among others. Particularly preferred are organic electroluminescent devices such as organic light emitting diodes, organic lasers, organic light emitting cells.

In certain particularly preferred embodiments, the organic electroluminescent device comprises a light-emitting layer comprising one of the organoboron compounds, or one of the organoboron compounds and one of the phosphorescent emitters, or one of the organoboron compounds and one of the TADF emitters, or one of the organoboron compounds and one of the fluorescent emitters, or one of the organoboron compounds and one of the host materials, or one of the organoboron compounds, one of the phosphorescent emitters and one of the host materials, or one of the organoboron compounds, one of the TADF emitters and one of the host materials.

In certain particularly preferred embodiments, the organic electroluminescent device comprises a light-emitting layer comprising one said organoboron polymer, or comprising one said organoboron polymer and one phosphorescent emitter, or comprising one said organoboron polymer and one TADF emitter, or comprising one said organoboron polymer and one fluorescent emitter, or comprising one said organoboron polymer and one host material, or comprising one said organoboron polymer, one phosphorescent emitter and one host material, or comprising one said organoboron polymer, one TADF emitter and one host material.

The electroluminescent device, in particular an OLED, as described above comprises a substrate, an anode, at least one light-emitting layer, and a cathode.

The substrate may be transparent, opaque, partially transparent. A transparent substrate may be used to fabricate a transparent light emitting device. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer, glass, or a composite thereof. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from a polymer film or plastic, having a glass transition temperature (T)_g) It is 150 ℃ or higher, preferably 200 ℃ or higher, more preferably 300 ℃ or higher, most preferably 350 ℃ or higher.

Examples of suitable flexible substrates are, but are not limited to, 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 the hole injection layer or the hole transport layer or the 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 the p-type semiconductor material as hole injection layer or hole transport layer or electron blocking layer is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include (but are not limited to): al, Cu, Au, A, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide, alloys of the above examples, and the like. Other alloys of anode materials are known and can be readily selected by one of ordinary skill in the art. The anode material may be deposited by any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam, and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and used to make the devices of the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the electron injection layer or the electron transport layer or the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the n-type semiconductor of the emitter or electron injection layer or electron transport layer or hole blocking layer in the light emitting layer is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2 eV. In principle all cathode materials that can be used in OLED devices are possible as cathode material according to the invention. Examples of cathode materials include (but are not limited to): al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited by any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam, and the like.

The OLED may also comprise further functional layers such as hole injection layers, hole transport layers, electron blocking layers, electron injection layers, electron transport layers, hole blocking layers. Suitable materials for use as these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of which are hereby incorporated by reference.

The organoboron mixture of one embodiment includes at least one organic functional material and the organoboron compound or organoboron polymer described above. In one embodiment, the organic functional material is selected from a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron blocking material, an electron transport material, an organic light emitting material, an organic host material, or a light emitting material.

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 the use of organic electronic devices comprising 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 will now be described in connection with preferred embodiments, but the invention is not limited to the embodiments described below. It is intended that the scope of the invention be covered by the appended claims. Those skilled in the art, having the benefit of this disclosure, will appreciate that certain modifications from the disclosed embodiments are intended to be covered by the spirit and scope of the appended claims.

Example 1

2.05g of Compound A, 1.00g of Compound B, 0.04g of copper powder, 3.32g of potassium carbonate, 0.16g of 18-crown-6 and 100mL of o-dichlorobenzene were reacted under heating and stirring at 180 ℃ for 3 days under a nitrogen atmosphere. And cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the reaction system, and washing a filter cake by using dichloromethane to obtain a filtrate. The filtrate was distilled under reduced pressure to remove methylene chloride and o-dichlorobenzene to give a crude product. The crude product was purified by silica gel column (eluting with dichloromethane and petroleum ether) to obtain 2.10g of Compound C. The yield was 92%. [ M ] A⁺]＝380。

Examples 2 to 6

Examples 2-6 similar synthetic procedures as in example 1 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

Example 7

2.39g of Compound D, 1.02g of Compound E, 0.04g of copper powder, 3.32g of potassium carbonate, 0.16g of 18-crown-6 and 100mL of o-dichlorobenzene were reacted under heating and stirring at 180 ℃ for 3 days under a nitrogen atmosphere. And cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the reaction system, and washing a filter cake by using dichloromethane to obtain a filtrate. The filtrate was distilled under reduced pressure to remove methylene chloride and o-dichlorobenzene to give a crude product. The crude product was purified by silica gel column (eluting with dichloromethane and petroleum ether) to obtain 2.30g of compound F. The yield was 87%. [ M ] A⁺]＝440。

Examples 8 to 13

Examples 8-13 similar synthetic procedures as in example 7 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

Example 14

5.5mL of phenylmagnesium bromide (2.2M in ether) was placed in 40mL of anhydrous oxygen-free tetrahydrofuran under nitrogen and stirred in a low temperature bath at-30 ℃ for 10 minutes. After 1.52G of Compound G was added to the reaction system, the reaction system was left to react at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with a small amount of water. The reaction system was suction filtered under reduced pressure and the filter cake was washed with ethanol. After drying the filter cake, placing the filter cake in 100mL of glacial acetic acid, and adding a catalytic amount of concentrated hydrochloric acid. The reaction was heated to 110 ℃ for 6 hours. After the reaction was completed, the temperature was lowered to room temperature. Reacting the systemPoured into 500mL of ice water. And (5) carrying out vacuum filtration to obtain a filter cake. The crude product was purified by silica gel column (eluting with dichloromethane and petroleum ether) to give 1.5g of compound H. The yield was 77%. [ M ] A⁺]＝486。

Examples 15 to 19

Examples 15-19 similar synthetic procedures as in example 14 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

Example 20

10.9mL of phenylmagnesium bromide (2.2M in ether) was placed in 60mL of anhydrous oxygen-free tetrahydrofuran under nitrogen and stirred in a low temperature bath at-30 ℃ for 10 minutes. After 1.75g of Compound I was added to the reaction system, the reaction system was left to react at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with a small amount of water. The reaction system was suction filtered under reduced pressure and the filter cake was washed with ethanol. After drying the filter cake, placing the filter cake in 100mL of glacial acetic acid, and adding a catalytic amount of concentrated hydrochloric acid. The reaction was heated to 110 ℃ for 6 hours. After the reaction was completed, the temperature was lowered to room temperature. The reaction was poured into 500mL of ice water. And (5) carrying out vacuum filtration to obtain a filter cake. The crude product was purified by silica gel column (eluting with dichloromethane and petroleum ether) to give 2.2g of Compound J. The yield was 85%. [ M ] A⁺]＝650。

Examples 21 to 26

Examples 21-26 similar synthetic procedures as in example 20 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

Example 27

Under nitrogen protection, 1.00g of Compound K was placed in 30mL of anhydrous, oxygen-free tetrahydrofuran and stirred in a low temperature bath at-78 ℃ for 10 minutes. 1.1mL (2.2M in tetrahydrofuran solution) of n-butyllithium was added dropwise, and the reaction was allowed to continue at-78 ℃ for 1 hour. After 0.78g of bis (trimethylphenyl) boron fluoride was added, the reaction system was left at room temperature to react for 12 hours. After the reaction was complete, a small amount of water was added to quench the reaction. The reaction system was distilled under reduced pressure to obtain a crude product, which was purified by silica gel column (eluting agents were dichloromethane and petroleum ether) to obtain 0.9g of compound L. The yield was 67%. [ M ] A⁺]＝655。

Examples 28 to 33

Examples 28-33 similar synthetic procedures as in example 27 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

Example 34

Under nitrogen protection, 1.00g of Compound M was placed in 30mL of anhydrous, oxygen-free tetrahydrofuran solution and stirred in a low temperature bath at-78 ℃ for 10 minutes. 0.8mL (2.2M) of n-butyllithium was added dropwise thereto, and the reaction system was allowed to stand at-78 ℃ for 1 hour. After 0.58g of bis (trimethylphenyl) boron fluoride was added, the reaction system was left at room temperature to react for 12 hours. After the reaction was complete, a small amount of water was added to quench the reaction. The reaction system was distilled under reduced pressure to obtain a crude product, which was purified by silica gel column (eluent was dichloromethane and petroleum ether) to obtain 0.7g of compound N. The yield was 56%. [ M ] A⁺]＝819。

Examples 35 to 40

Examples 35-40 similar synthetic procedures as in example 34 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products are now listed in the table, along with the corresponding mass spectrometric measurements and yields.

EXAMPLE 41

1.0g of compound O, 0.2g of compound P, 0.1g of tris (dibenzylideneacetone) dipalladium, 0.8g of sodium tert-butoxide, 0.06g of tri-tert-butylphosphine tetrafluoroborate and 30mL of toluene are heated with stirring to 110 ℃ for 12 hours under nitrogen protection. After the reaction was completed, the temperature was lowered to room temperature. The reaction system was filtered under reduced pressure through celite, and the celite was rinsed with dichloromethane. The organic liquid phase was concentrated by distillation under reduced pressure to give a crude product, which was purified by silica gel column (eluting agents were dichloromethane and petroleum ether) to give 0.8g of compound Q. The yield was 78%. [ M ] A⁺]＝473。

1.0g of Compound Q, 0.68g of Compound R, 0.13g of copper powder, 0.06g of 18-crown-6, 0.44g of potassium carbonate and 30mL of o-dichlorobenzene were reacted under nitrogen atmosphere by heating to 180 ℃ with stirring for 72 hours. After the reaction was completed, the temperature was lowered to room temperature. The reaction system was suction filtered under reduced pressure and washed with dichloromethane. The organic liquid phase was concentrated by distillation under reduced pressure to give a crude product, which was purified by silica gel column (eluting agents were dichloromethane and petroleum ether) to give 0.92g of compound S. The yield was 65%. [ M ] A⁺]＝666。

1.0g of Compound S is dissolved in 20mL of tetrahydrofuran under nitrogen. This was added to 4.1mL (2.2M) of methylmagnesium bromide at-78 ℃. After stirring for 10 minutes, the reaction was left at room temperature and the reaction was continued for 6 hours. After the reaction was completed, a small amount of water was added to quench the reaction. And removing the solvent from the reaction system by vacuum filtration to obtain an intermediate. The intermediate is dried in vacuum and dissolved in 100mL of glacial acetic acid, stirred and heated to 110 ℃, and then added with a catalytic amount of concentrated hydrochloric acid to continue the reaction for 6 hours. After the reaction was completed, the temperature was lowered to room temperature. The reaction system was poured into ice water. The crude product was obtained after vacuum filtration and purified by silica gel column (eluent dichloromethane and petroleum ether) to obtain 0.4g of compound T. The yield was 40%. [ M ] A⁺]＝666。

Examples 42 to 46

Examples 42-46 similar synthetic procedures as in example 41 were used, with only the reactants being replaced with the corresponding reactants. The corresponding reactants and target products and the corresponding mass spectrometric measurements are now listed in the table.

Because the organic boron derivative has a plurality of bridge bonds, the molecule has stronger rigidity and can have narrower luminescence spectrum; meanwhile, due to the matched single triplet state energy level, the material has a luminescence mechanism of thermal activation delayed fluorescence, the maximum external quantum efficiency of more than 5% can be realized in an electroluminescent device, and meanwhile, the luminescent color purity of the electroluminescent device is high (the half-peak width of a spectrum is less than 80nm) due to the rigid molecular structure of the material.

The invention also provides an organic electroluminescent device prepared based on the organic boron derivative, which comprises a cathode, an anode and an organic thin film layer, wherein the organic thin film layer is arranged between the cathode and the anode, the organic thin film layer comprises at least one organic light-emitting layer, the organic thin film layer contains the organic boron derivative, and the organic light-emitting layer is preferably prepared from the organic light-emitting material.

The organic electroluminescent device is provided with the anode, the hole injection layer, the hole transport layer, the electron blocking layer, the organic luminescent layer, the exciton blocking layer, the electron transport layer, the electron injection layer and the cathode in sequence from the height direction.

Next, the organic electroluminescent element of the present invention will be explained.

The glass plate coated with the ITO transparent conductive layer is subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, washed in acetone and ethanol for three times respectively, baked in a clean environment to completely remove moisture, washed by ultraviolet light and ozone, and bombarded on the surface by low-energy cation beams. Placing ITO conductive glass into a vacuum chamber, and vacuumizing to less than 5 × 10^-4Pa. Using ITO conductive glass as an anode, and sequentially evaporating a Hole Injection Layer (HIL), a hole transport layer (HIL), an Electron Blocking Layer (EBL), an organic light emitting layer (EML), an Electron Transport Layer (ETL) and a cathode on the ITO conductive glass; wherein, the evaporation rate of the organic material is 0.2nm/s, and the evaporation rate of the metal electrode is 0.5 nm/s.

The electroluminescence spectra were collected using a photon multichannel analyzer PMA-12(Hamamatsu C10027-01), which can be detected in the spectral region of 200 and 950 nm. The external quantum efficiency of the device was obtained by measuring the forward light intensity using an integrating sphere (Hamamatsu a 10094). All measurements were performed at room temperature in an atmospheric environment.

The method for forming each structural layer in the organic electroluminescent device of the present invention is not particularly limited, and conventional vacuum evaporation methods, spin coating methods, and the like; meanwhile, the materials used for the structural layers in the electroluminescent device of the present invention are also not particularly limited, and the device structures in the examples are merely to illustrate the characteristics of the organoboron derivatives of the present invention.

Example 47

The compound of the present invention is purified by high-purity sublimation by a conventional method, and then an organic light-emitting device is manufactured by the following method.

Thinly coated with a thickness of

The glass substrate of Indium Tin Oxide (ITO) of (a) was put in distilled water in which a detergent was dissolved and subjected to ultrasonic washing. After washing ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes using distilled water, and then ultrasonic washing was performed using isopropyl alcohol, acetone, and a methanol solvent, and drying was performed. The substrate is then transferred to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.

A hot vacuum press of 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) of the following formula is applied to the transparent ITO electrode thus prepared to a thickness of

As a hole injection layer.

The following compounds as materials for transporting holes were compoundedThe compound 4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline](TAPC)

Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.

Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was used

Vacuum depositing on the hole transport layer to form an electron blocking layer.

Then, the following compound 1 and bis [2- ((oxo) diphenylphosphino) phenyl group were reacted]Ether (DPEPO) was vacuum deposited on the electron blocking layer at a weight ratio of 2:8 and a thickness of

Thereby forming a light emitting layer.

Then, the following bis [2- ((oxo) diphenylphosphino) phenyl group]Ether (DPEPO) is deposited on the light-emitting layer in a vacuum to a thickness of

Thereby forming an exciton blocking layer.

1, 3, 5-tris [ (3-pyridyl) -3-phenyl ] materials which transport electrons]Benzene (TmPyPB)

Vacuum depositing on the luminescent layer to a thickness of

An electron transport layer is formed.

Reacting the compound 8-hydroxyquinoline lithium (Liq)

And metallic aluminum

Are sequentially deposited on the electron transport layer as an electron injection layer and a cathode.

In the above process, the deposition rate of the hole injection layer material HAT-CN and the electron injection layer material Liq is kept at

To

The deposition rate of the organic functional layer material, including hole transport layer material, electron barrier layer material, luminescent layer material and electron transport layer material, is maintained at

To

The deposition rate of the electrode material metallic aluminum is kept at

To

And the vacuum degree during deposition is maintained at 1X 10^-7Hold in the palm to 5 x 10^-6And thus an organic light emitting device is manufactured.

Examples 48 to 53

Examples 48 to 53 Using the same preparation conditions and procedures as in example 47, only Compound 1 of the light-emitting layer was replaced with the corresponding organoboron derivative of the invention. The corresponding compounds and corresponding device parameters are now listed in the table.

From examples 47 to 53, it is understood that the organoboron compound of the present invention can achieve high efficiency and high color purity in an electroluminescent device.

The features of the above-described exemplary embodiments may be arbitrarily combined, and for the sake of brevity, all possible combinations of the features in the above-described exemplary embodiments are not described in detail, but should be construed as falling within the scope of the present description as long as there is no contradiction between the combinations of the features.

The above-described exemplary embodiments merely represent several embodiments of the present invention, which are described in more detail and detail, but are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. An organoboron compound, characterized in that the structure of the organic compound is selected from any one of the general formulae (1), (2), (3), (4), (5) or (6):

ar is¹～Ar⁵Having R on the ring of the radical¹Group R¹The groups are the same or different at each occurrence; the R is¹The group is selected from H, D, linear alkanes having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, thioalkoxy groups having 1 to 20 carbon atoms, branches having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, silyl groups having 3 to 20 carbon atoms, keto groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms, cyano groups, carbamoyl groups, haloformyl groups, formyl groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, nitro groups, ester groups, trifluoromethyl groups, Cl, Br, I, F, crosslinkable groups, a substituted or unsubstituted aromatic or heteroaromatic ring system containing 5 to 40 ring atoms, having one or more substituted or unsubstituted aryloxy or heteroaryloxy groups containing 5 to 40 ring atoms;

2. According to the rightThe organoboron compound of claim 1, wherein Ar is¹～Ar⁵Each group is independently selected from any one of the following groups:

wherein when there are plural X groups in the same group, each of the X groups is independently N or CR². When there are plural Y groups in the same group, each of the Y groups is independently selected from CR³R⁴，SiR³R⁴，NR³，BR³，C(＝O)，S(＝O)，S(＝O)₂S or O.

3. The organoboron compound of claim 2, where in the Y group, R²Radical, R³Radical, R⁴Definition of radicals and said R¹The groups are the same.

4. The organoboron compound of claim 1, where A is¹～A⁵Each group is independently connected to its neighboring group with a single bond or a double bond.

5. An organoboron compound according to claim 1 or 4, characterized in that A is¹～A⁵Each group is independently selected from any one of the following groups:

wherein Ar is⁶Radical, Ar⁷Radicals with said Ar¹～Ar⁵The radicals are defined identically; the dotted line represents a bond to an adjacent group.

6. The organoboron compound of claim 1, wherein the organoboron compound has a structure represented by the general formulae (7) to (12):

wherein, the benzene ring in the general formula has the R¹Group R¹The groups may be the same or different at each occurrence.

7. An organoboron polymer, wherein the repeating units of the organoboron polymer comprise the organoboron compound of any of claims 1 to 6.

8. An organoboron mixture comprising the organoboron compound of any one of claims 1 to 6 or the organoboron polymer of claim 7 and at least one organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, a light emitting material and a host material.

9. An organic electronic device comprising the organoboron compound of any one of claims 1 to 6 or the organoboron polymer of claim 7 or the organoboron mixture of claim 8.

10. The organic electronic device according to claim 9, wherein the organic electronic device has a light-emitting layer made of any one of the organoboron compound, the organoboron polymer, or the organoboron mixture.