CN111410952A - Organic electroluminescent material containing boron and application thereof in organic electroluminescent device - Google Patents

Organic electroluminescent material containing boron and application thereof in organic electroluminescent device Download PDF

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CN111410952A
CN111410952A CN201910012073.5A CN201910012073A CN111410952A CN 111410952 A CN111410952 A CN 111410952A CN 201910012073 A CN201910012073 A CN 201910012073A CN 111410952 A CN111410952 A CN 111410952A
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organic electroluminescent
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李崇
王芳
殷梦轩
叶中华
谢丹丹
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention relates to a boron-containing organic electroluminescent material and application thereof in an organic electroluminescent device, belonging to the technical field of semiconductors, and the structure of the compound provided by the invention is shown as a general formula (1):
Figure DDA0001937701240000011
the compound is composed of boron-containing groups, and has the characteristics of strong rigidity of the groups, difficult intermolecular crystallization and aggregation and good film forming property. When the compound is used as a luminescent layer material of an organic electroluminescent device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improvedIt is good; meanwhile, the service life of the device is obviously prolonged.

Description

Organic electroluminescent material containing boron and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to a boron-containing organic electroluminescent material and application thereof in an organic electroluminescent device.
Background
The Organic electroluminescent (O L ED: Organic L light Emission Diodes) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect.
The O L ED light-emitting device is just like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, wherein the different functional materials are mutually overlapped to form the O L ED light-emitting device according to the application.
However, the conventional organic fluorescent materials can emit light only by using 25% singlet excitons formed by electric excitation, the internal quantum efficiency of the device is low (up to 25%), the external quantum efficiency is generally lower than 5%, and there is a great difference from the efficiency of a phosphorescent device, although the intersystem crossing is enhanced by the strong spin-orbit coupling of heavy atom centers of the phosphorescent material, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, and the internal quantum efficiency of the device reaches 100%.
The materials generally have small singlet-triplet energy level difference (△ EST), triplet excitons can be converted into singlet excitons through intersystem crossing to emit light, the singlet excitons and the triplet excitons formed under electric excitation can be fully utilized, the internal quantum efficiency of the device can reach 100 percent, meanwhile, the materials have controllable structures, stable properties, low price and no need of precious metals, and have wide application prospects in the field of O L EDs.
Although TADF materials can theoretically achieve 100% exciton utilization, there are actually the following problems: (1) the T1 and S1 states of the designed molecule have strong CT characteristics, and a very small energy gap of S1-T1 state can realize high conversion rate of T1 → S1 state excitons through a TADF process, but simultaneously lead to low radiation transition rate of S1 state, so that the high exciton utilization rate and the high fluorescence radiation efficiency are difficult to realize at the same time; (2) even though doped devices have been employed to mitigate the T exciton concentration quenching effect, most devices of TADF materials suffer from severe roll-off in efficiency at high current densities.
In terms of the actual demand of the current O L ED display lighting industry, the development of the O L ED material is still far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop higher-performance organic functional materials as a material enterprise.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a boron-containing organic electroluminescent material and an application thereof in an organic electroluminescent device, the compound can be used as a luminescent layer doping material to be applied to the manufacture of an O L ED luminescent device, and the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved.
The technical scheme of the invention is as follows: an organic electroluminescent material containing boron, the structure of the compound is shown as general formula (1):
Figure BDA0001937701220000021
in the general formula (1), X1、X2、X3Independently represent a sulfur atom, an oxygen atom,
Figure BDA0001937701220000022
N(R5)、B(R6) Or C (R)7)(R8)，X3May also represent a single bond; wherein R is7And R8Can be connected with each other to form a ring;
a. b and c are respectively and independently 0 or 1;
R1-R4each independently represents a hydrogen atom, a substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C2-20Alkenyl of (a), substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, C6-30Aryl or 5 to 30 membered heteroaryl substituted amino, substituted or unsubstituted styryl; and R is1And R2、R3And R4Can be connected with each other to form a 5-30 membered ring or a heterocyclic ring;
z is1-Z5Each independently represents a nitrogen atom or C-Ri(ii) a Wherein i represents 1, 2, 3 or 4;
the R is5-R8Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms;
the R isiEach independently represents a hydrogen atom, a cyano group, deuterium, a halogen atom, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms; and at least one RiNot represented as a hydrogen atom;
the substituents of said substitutable groups are optionally selected from protium, cyano, halogen, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, RiEach independently represents a hydrogen atom, deuterium, cyano, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted naphthylSubstituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted azabenzophenanthryl, a structure represented by general formula (2), general formula (3) or general formula (4);
Figure BDA0001937701220000031
z represents a nitrogen atom or a carbon atom; z at the attachment site is represented as a carbon atom;
the L, L1、L2Each independently represents a single bond, a substituted or substituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrenylene group, or a substituted or unsubstituted benzophenanthrylene group;
s, t and n are respectively and independently 0, 1 or 2;
the R isa、Rb、RcEach independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms; ra、Rb、RcThe connection mode with the general formula (2) or the general formula (3) includes two modes of ring merging and substitution;
each A, B independently represents a substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms;
said X4、X5、X6Each independently represents a single bond, -O-, -S-, -C (R)16)(R17) -or-N (R)18) -, and X4、X5Not simultaneously represent a single bond; r16And R17Can be connected with each other to form a ring;
the R is16-R18Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms;
the substituent of the substitutable group is selected from deuterium, cyano, halogen and C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, R isa、Rb、RcEach independently represents a hydrogen atom, deuterium, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted azacarbazolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted benzopyrolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted benzindene group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenyl group, Substituted or unsubstituted benzophenanthryl, substituted or unsubstituted azabenzophenanthryl;
a, B are respectively and independently represented by substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted anthryl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzophenanthryl, and substituted or unsubstituted azabenzophenanthryl;
the R is1-R4Each independently represents one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenoxy group, a substituted or unsubstituted phenyl group, a methoxy group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenylamino group, and a substituted or unsubstituted vinyl group;
the R is5-R8、R16-R18Each independently represents one of methyl, ethyl, propyl, isopropyl, tertiary butyl, amyl, phenyl, naphthyl, biphenyl, pyridyl or furyl;
the substituent of the substitutable group is one or more selected from deuterium, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group or furyl group.
More preferably, the general formula (1) may be represented by a structure represented by general formula (5), general formula (6), general formula (7), general formula (9), general formula (10) or general formula (11);
Figure BDA0001937701220000041
Figure BDA0001937701220000051
the R is19、R20Each independently represents one of phenyl, pyridyl, naphthyl, naphthyridinyl, pyridyl, biphenyl, terphenyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl.
Further preferably, R is1And R2、R3And R4At least one is formed intoAnd (4) a ring.
Further preferably, at least one of a, b and c is 1.
Further preferably, R isiAt least one of the structures is represented by a general formula (2), a general formula (4) or a general formula (5).
Further preferably, the specific structure of the general formula (1) is:
Figure BDA0001937701220000052
Figure BDA0001937701220000061
Figure BDA0001937701220000071
Figure BDA0001937701220000081
Figure BDA0001937701220000082
one kind of (1).
The second invention of the invention provides the application of the organic electroluminescent material containing boron in the preparation of organic electroluminescent devices.
A third aspect of the present invention provides an organic electroluminescent device comprising at least one functional layer comprising a boron-containing organic electroluminescent material.
A fourth aspect of the present invention is to provide an organic electroluminescent device comprising a light-emitting layer containing a boron-containing organic electroluminescent material.
It is further preferable to provide an organic electroluminescent device in which a boron-containing organic electroluminescent material is used as a doping material for the light-emitting layer.
A fifth aspect of the invention provides a lighting or display element comprising said organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound has stronger molecular group rigidity, can avoid intermolecular aggregation, and patents CN107851724A and WO2017/188111A1 disclose a boron-containing compound and application thereof, because D-A formed by the compound is weaker, the overlap of front tracks between a boron-containing system and an electron donor connected with the boron-containing system is larger, the energy level difference between an S1 state and a T1 state is larger, and the delay life is longer, while the boron-containing heterocyclic system has strong electron-withdrawing effect, so that the overlap of the front tracks between the electron donors connected with the boron-containing heterocyclic system is smaller, and the small energy level difference between an S1 state and a T1 state is realized, thereby realizing reverse intersystem crossing under the condition of thermal stimulation; the boron-containing compound has a certain dihedral angle formed by the D-A and is connected with other branched chain structures, so that the crystallinity of molecules can be damaged, the intermolecular aggregation is avoided, the boron-containing compound has good film forming property and fluorescence quantum efficiency, and is suitable for being used as a luminescent layer doping material;
the compound can be used as a luminescent layer doping material to be applied to the manufacture of an O L ED luminescent device, good device performance is obtained, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved, and meanwhile, the service life of the device is obviously prolonged.
The compound material has good application effect in an O L ED light-emitting device and good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an O L ED device using the materials listed in the present invention;
FIG. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a comparative device.
In the drawings: 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is hole transport, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is an electron transport or hole blocking layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
In this context, all percentages are by weight unless otherwise indicated; unless otherwise stated, the operation was carried out at normal temperature and normal pressure.
All materials in the following examples were purchased from energy saving, Wangrun GmbH.
Example 1: synthesis of intermediate C:
Figure BDA0001937701220000101
adding 0.01mol of raw material A1, 0.012mol of raw material B1, 0.03mol of CsOH and 150ml of DMSO into a 250ml three-neck flask under the protection of nitrogen, adding oil bath into the mixture at 150 ℃ for reaction for 15h, tracking the reaction by GC-MS or T L C, passing the product through a neutral silica gel column after the reaction is finished, eluting by V (petroleum ether): V (ethyl acetate ═ 20:1 to obtain an intermediate A1, wherein the yield is 82%20H12Br2O) theoretical value of C,56.11, H,2.83, Br,37.33, test value of C,56.12, H,2.82, Br,37.32 and HP L C-MS, material molecular weight of 425.93 and measured molecular weight of 425.98.
Figure BDA0001937701220000102
A250 ml three-necked flask was charged with 0.01mol of intermediate A1 and 0.025mol of raw material C1 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.04mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, passing through a silica gel column to obtain a target product intermediate B1, wherein the purity of HP L C is 98.5%, the yield is 42.5%, and an elemental analysis structure (molecular formula C)26H15ClO) theoretical C,82.43, H,3.99, Cl,9.36, test value C,82.41, H,3.98, Cl,9.38, HP L C-MS theoretical 378.08, found 378.12.
Figure BDA0001937701220000103
Adding 0.01mol of intermediate B1, 0.015mol of tert-butyl lithium and 150ml of tert-butyl benzene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, heating to 60 ℃, stirring and reacting for 2 hours, then naturally cooling to room temperature, dropwise adding 0.015mol of BBr3 and 0.1mol of diisopropylethylamine, stirring and reacting for 1 hour at room temperature, taking a sample point plate, indicating that no intermediate B1 remains, completely reacting, adding water and dichloromethane for extraction and liquid separation, taking an organic phase, adding anhydrous magnesium sulfate for water removal, filtering, carrying out reduced pressure rotary evaporation on the filtrate at (-0.09MPa, 25 ℃) to obtain an intermediate C1, wherein the purity of the HP L C is 98.5%, the yield is 55.7%, and passing through a neutral silica gel column to obtain an element analysis structure (molecular formula C is C26H13BO) theoretical C,88.67, H,3.72, B,3.07, test value C,88.65, H,3.73, B,3.08 HP L C-MS theoretical 352.11, found 352.14.
The intermediate synthesized by the above synthetic route comprises:
Figure BDA0001937701220000111
example 2: synthesis of intermediate E:
Figure BDA0001937701220000112
a250 ml three-necked flask was charged with 0.01mol of D1 as a starting material, 0.012mol of E1 as a starting material, 0.03mol of sodium tert-butoxide, 1 × 10 and under a nitrogen atmosphere-4mol Pd2(dba)3，1×10-4Heating and refluxing 150ml of tri-tert-butylphosphine and 150ml of toluene for 24 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product intermediate D1, wherein the purity of HP L C is 99.8%, the yield is 84.9%, and an elemental analysis structure (molecular formula C is34H33Br2N) theoretical C,66.35, H,5.40, N,2.28, Br,25.97, test value C,66.33, H,5.41, N,2.27, Br,25.967, HP L C-MS, theoretical 613.10, found 613.12.
Figure BDA0001937701220000121
A250 ml three-necked flask was charged with 0.01mol of intermediate D1 and 0.025mol of raw material C1 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.04mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, passing through a silica gel column to obtain a target product intermediate E1, wherein the purity of HP L C is 98.8%, the yield is 55.4%, and an elemental analysis structure (molecular formula C)40H36ClN) theoretical value C,84.86, H,6.41, Cl,6.26, N,2.47, test value C,84.84, H,6.40, Cl,6.27, N,2.48, HP L C-MS, theoretical value 565.25, found value 565.31.
The intermediate synthesized by the above synthetic route comprises:
Figure BDA0001937701220000122
example 3: synthesis of intermediate G:
Figure BDA0001937701220000131
a250 ml three-necked flask was charged with 0.01mol of F1 as a starting material and 0.025mol of C3 as a starting material under a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.04mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product intermediate F1, wherein the purity of HP L C is 98.4%, and the yield is 47.9%.
Elemental analysis Structure (molecular formula C)47H55Cl) theoretical C,86.13, H,8.46, Cl,5.41, test value C,86.13, H,8.46, Cl,5.41, HP L C-MS theoretical 654.40, found 654.47.
Figure BDA0001937701220000132
Adding 0.01mol of intermediate F1, 0.015mol of tert-butyl lithium and 150ml of tert-butyl benzene into a 250ml three-necked bottle, stirring and mixing under the protection of nitrogen, heating to 60 ℃, stirring and reacting for 2 hours, then naturally cooling to room temperature, dropwise adding 0.015mol of BBr3 and 0.1mol of diisopropylethylamine, stirring and reacting for 1 hour at room temperature, taking a sample point plate, indicating that no intermediate F1 remains and completely reacting, adding water and dichloromethane for extraction and liquid separation, taking an organic phase, adding anhydrous magnesium sulfate for water removal, filtering, carrying out reduced pressure rotary evaporation on the filtrate at (-0.09MPa and 25 ℃), passing through a neutral silica gel column to obtain an intermediate G1, wherein the purity of HP L C is 99.1%, and the yield is 58.2%;
elemental analysis Structure (molecular formula C)39H37B) Theoretical C,90.69, H,7.22, B,2.09, test value C,90.68, H,7.23, B,2.08 HP L C-MS, theoretical 516.30, found 516.36.
The intermediate synthesized by the above synthetic route comprises:
Figure BDA0001937701220000133
example 4: synthesis of intermediate I:
Figure BDA0001937701220000141
a250 ml three-necked flask was charged with 0.01mol of G1 as a starting material and 0.012mol of H3 as a starting material under a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.02mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0001mol of Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, passing through a silica gel column to obtain a target product intermediate H1, wherein the purity of HP L C is 99.3%, the yield is 65.4%, and an elemental analysis structure (molecular formula C)33H21Cl): theoretical value C, 87.50; h, 4.67; cl, 7.83; test values are: c, 87.51;h,4.66, Cl,7.85, HP L C-MS, theoretical 452.13, found 452.18.
Figure BDA0001937701220000142
Adding 0.01mol of intermediate H1, 0.015mol of tert-butyl lithium and 150ml of tert-butyl benzene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, heating to 60 ℃, stirring and reacting for 2 hours, then naturally cooling to room temperature, dropwise adding 0.015mol of BBr3 and 0.1mol of diisopropylethylamine, stirring and reacting for 1 hour at room temperature, taking a sample point plate, indicating that no intermediate H1 remains and completely reacting, adding water and dichloromethane for extraction and liquid separation, taking an organic phase, adding anhydrous magnesium sulfate for water removal, filtering, carrying out reduced pressure rotary evaporation on the filtrate at (-0.09MPa, 25 ℃) to obtain an intermediate I1, wherein the purity of HP L C is 98.3%, the yield is 53.7%, and an element analysis structure (molecular formula C is C33H19B) Theoretical values of C,92.97, H,4.49, B,2.54, test values of C,92.98, H,4.47, B,2.53, HP L C-MS, theoretical value of 426.16, found value of 426.21.
The intermediate synthesized by the above synthetic route comprises:
Figure BDA0001937701220000143
Figure BDA0001937701220000151
example 5: synthesis of Compound 1:
Figure BDA0001937701220000152
0.01mol of intermediate C1, 200ml of dichloromethane and 0.03mol of tert-chlorobutane are added into a three-neck flask with the thickness of 250m L, the temperature is reduced to 0-5 ℃, and 0.03mol of anhydrous AlCl is added3Reacting for 2-5 hours, completely reacting, extracting with dichloromethane after hydrolysis, and separating liquid; adding anhydrous magnesium sulfate into organic phase, removing water, filtering, performing rotary evaporation under reduced pressure (0.09 MPa, 25 deg.C), and passing through neutral silica gelColumn chromatography to obtain target product compound 5, HP L C with purity of 99.1% and yield of 52.5%, and element analysis structure (molecular formula C)34H29BO) theoretical C,87.93, H,6.29, B,2.33, test value C,87.95, H,6.28, B,2.34, HP L C-MS theoretical 464.23, found 464.27.
Example 6: synthesis of Compound 2:
Figure BDA0001937701220000153
prepared according to the synthetic method for compound 1 in example 5, except that intermediate G1 is substituted for intermediate C1; elemental analysis Structure (molecular formula C)47H53B) Theoretical values of C,89.78, H,8.50, B,1.72, test values of C,89.76, H,8.51, B,1.73 and HP L C-MS, wherein the molecular weight of the material is 628.42, and the measured molecular weight is 628.42.
Example 7: synthesis of compound 9:
Figure BDA0001937701220000161
dissolving 0.01mol of intermediate C1 and 150m L dichloromethane in a three-neck flask with the volume of 250m L, stirring at room temperature (20-25 ℃), adding 0.03mol of NBS (N-bromosuccinimide) in batches, observing the reaction by using thin-layer chromatography (T L C) until the reaction is complete, pouring the reaction mixture into 200m L water, stirring for 2 hours, extracting with dichloromethane, separating, taking an organic phase, adding anhydrous magnesium sulfate to remove water, filtering, performing reduced pressure rotary evaporation (0.09 MPa, 25 ℃) on the filtrate, passing through a neutral silica gel column to obtain intermediate X1, HP L C with the purity of 98.6 percent and the yield of 51.1 percent, and analyzing an element structure (molecular formula C)26H11BBr2O): theoretical value C, 61.23; h, 2.17; b, 2.12; br, 31.34; test values are: c, 61.24; h, 2.16; b, 2.11; br, 31.33. ESI-MS (M/z) (M +): theoretical value is 507.93, found 507.95.
Figure BDA0001937701220000162
Under nitrogen atmosphere, inA250 m L three-neck flask was charged with 0.02mol of the prepared intermediate X1, 0.05mol of the starting material X1, 0.06mol of sodium tert-butoxide, 2.5 × 10-5mol Pd2(dba)3And 2.5 × 10-5And (2) adding 150m of L toluene into the mixture to dissolve the tri-tert-butylphosphine, heating the mixture to 100 ℃, refluxing the mixture for 24 hours, observing the reaction by utilizing T L C until the reaction is complete, naturally cooling the mixture to room temperature, filtering the mixture, and rotatably steaming the filtrate until no fraction is produced, wherein the obtained substance is purified by a silica gel column to obtain the compound 9, the purity of the compound is 99.5%, and the yield of the compound is 45.8%.
Elemental analysis Structure (molecular formula C)50H31BN2O): theory C, 87.46; h, 4.55; b, 1.57; n, 4.08; test values are: c, 87.47; h, 4.54; b, 1.56; and N, 4.09. ESI-MS (M/z) (M +): theoretical value is 686.25, found 686.32.
Example 8: synthesis of compound 10:
Figure BDA0001937701220000163
a250 ml three-necked flask was charged with 0.01mol of intermediate C2 and 0.012mol of starting material X2 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.02mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0001mol of Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, passing through a silica gel column to obtain a target product compound 10, wherein the purity of HP L C is 99.5%, the yield is 61.7%, and an elemental analysis structure (molecular formula C)38H19BO2) Theoretical value of 88.05, H,3.69, B,2.09, test value of 88.04, H,3.71, B,2.08, HP L C-MS, theoretical value of 518.15, found value of 518.23.
Example 9: synthesis of compound 21:
Figure BDA0001937701220000171
prepared according to the synthetic method of compound 1 in example 5, except that intermediate I1 is used instead of intermediate C1, iodomethane is usedAlkyl instead of tert-butyl chloride; elemental analysis Structure (molecular formula C)35H23B) Theoretical values of C,92.52, H,5.10, B,2.38, test values of C,92.54, H,5.09, B,2.37, HP L C-MS, material molecular weight of 454.19 and actual measured molecular weight of 454.24.
Example 10: synthesis of compound 35:
Figure BDA0001937701220000172
adding 0.01mol of raw material X3, 0.015mol of tert-butyl lithium and 150ml of tert-butyl benzene into a 250ml three-mouth bottle under the protection of nitrogen, stirring and mixing, heating to 60 ℃, and stirring for reacting for 2 hours; then naturally cooled to room temperature, and 0.015mol BBr is added dropwise3And 0.1mol of diisopropylethylamine, stirring and reacting for 1 hour at room temperature, taking a sample, indicating that no raw material X3 remains, completely reacting, adding water and dichloromethane for extraction and liquid separation, taking an organic phase, adding anhydrous magnesium sulfate for water removal, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 25 ℃), passing through a neutral silica gel column to obtain the compound 35, wherein the purity of HP L C is 99.3%, the yield is 42.5%, and an elemental analysis structure (molecular formula C)36H27B) Theoretical values of C,91.92, H,5.79, B,2.30, test values of C,91.91, H,5.78, B,2.32, HP L C-MS, theoretical value of 470.22, found value of 470.35.
Example 11: synthesis of compound 41:
Figure BDA0001937701220000173
prepared according to the synthetic method for compound 35 in example 10, except that intermediate E1 is substituted for starting material X3; elemental analysis Structure (molecular formula C)40H34BN) theoretical value of C,89.05, H,6.35, B,2.00, N,2.60, test value of C,89.075, H,6.36, B,2.02, N,2.61, HP L C-MS, material molecular weight of 539.28 and measured molecular weight of 539.36.
Example 12: synthesis of compound 45:
Figure BDA0001937701220000181
a250 ml three-necked flask was charged with 0.01mol of Y2 as a starting material and 0.012mol of Y1 as a starting material under a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.02mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0001mol of Pd (PPh) was added3)4Heating and refluxing for 15 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate Y1, wherein the purity of HP L C is 98.3%, the yield is 79.2%, and an elemental analysis structure (molecular formula C)33H22Br2N2) Theoretical values of C,65.37, H,3.66, Br,26.36, N,4.62, test values of C,65.35, H,3.67, Br,26.35 and N,4.64, HP L C-MS are 604.01 and measured value is 604.11.
Figure BDA0001937701220000182
A250 ml three-necked flask was charged with 0.01mol of intermediate Y1 and 0.025mol of raw material Y3 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (90ml of toluene and 45ml of ethanol), and then charged with 0.04mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4Heating and refluxing for 20 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate Y2, wherein the purity of HP L C is 98.1%, and the yield is 43.1%.
Elemental analysis Structure (molecular formula C)43H33ClN2) Theoretical values of C,84.23, H,5.42, Cl,5.78, N,4.57, test values of C,84.24, H,5.43, Cl,5.77, N,4.56, HP L C-MS, theoretical value of 612.23, found value of 612.35.
Figure BDA0001937701220000183
Adding 0.01mol of intermediate Y2, 0.015mol of tert-butyl lithium and 150ml of tert-butyl benzene into a 250ml three-mouth bottle under the protection of nitrogen, stirring and mixing, heating to 60 ℃, and stirring for reacting for 2 hours; however, the device is not suitable for use in a kitchenThen naturally cooled to room temperature, and 0.015mol of BBr is added dropwise3And 0.1mol of diisopropylethylamine, stirring and reacting for 1 hour at room temperature, taking a sample point plate to show that no intermediate Y2 remains and the reaction is complete, adding water and dichloromethane for extraction and liquid separation, taking an organic phase, adding anhydrous magnesium sulfate for water removal, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 25 ℃), passing through a neutral silica gel column to obtain a compound 45, wherein the purity of HP L C is 99.5%, the yield is 35.7%, and an elemental analysis structure (molecular formula C)43H31BN2) Theoretical values of C,88.05, H,5.33, B,1.84, N,4.78, test values of C,88.04, H,5.32, B,1.83, N,4.79, HP L C-MS are 586.54, and actual value is 586.63.
Example 13: synthesis of compound 64:
Figure BDA0001937701220000191
prepared according to the synthetic method of compound 35 in example 10, except that the starting material X3 was replaced with the starting material X4;
Figure BDA0001937701220000192
prepared according to the synthetic method for compound 9 in example 7, except that intermediate X2 is substituted for starting material C1; elemental analysis Structure (molecular formula C)54H37BN2): theory C, 89.50; h, 5.15; b, 1.49; n, 3.87; test values are: c, 89.52; h, 5.14; b, 1.48; and N, 3.86. ESI-MS (M/z) (M +): theoretical value is 724.30, found 724.41.
Example 14: synthesis of compound 65:
Figure BDA0001937701220000193
prepared according to the synthetic method for compound 1 in example 5, except that intermediate X2 is substituted for intermediate C1; elemental analysis Structure (molecular formula C)34H27B) Theoretical values of C,91.48, H,6.10, B,2.42, test values of C,91.47, H,6.12, B,2.41, HP L C-MS and material moleculesThe amount was 446.22, the measured molecular weight was 446.34.
Example 15: synthesis of compound 81:
Figure BDA0001937701220000201
0.01mol of the prepared intermediate C3, 0.015mol of the raw material X5, 0.03mol of sodium tert-butoxide and 1 × 10 mol are added into a 250m L three-neck flask under a nitrogen atmosphere-5mol Pd2(dba)3And 1 × 10-5And (2) adding 150m of L toluene into the mixture to dissolve the tri-tert-butylphosphine, heating the mixture to 100 ℃, refluxing the mixture for 20 hours, observing the reaction by utilizing T L C until the reaction is complete, naturally cooling the mixture to room temperature, filtering the mixture, and carrying out rotary evaporation on the filtrate until no fraction is obtained, wherein the obtained substance is purified by a silica gel column to obtain the compound 81, the purity of the compound is 99.3%, and the yield of the compound is 56.7%.
Elemental analysis Structure (molecular formula C)50H42BNO): theory C, 87.84; h, 6.19; b, 1.58; n, 2.05; test values are: c, 87.86; h, 6.17; b, 1.57; and N, 2.06. ESI-MS (M/z) (M +): theoretical value is 683.34, found 683.42.
Example 16: synthesis of compound 98:
Figure BDA0001937701220000202
prepared according to the synthetic method of compound 35 in example 10, except that the starting material X3 was replaced with the starting material Z1; elemental analysis Structure (molecular formula C)27H14BNO2): theory C, 82.05; h, 3.57; b, 2.74; n, 3.54; test values are: c, 82.04; h, 3.58; b, 2.75; and N, 3.53. ESI-MS (M/z) (M +): theoretical value is 395.11, found 395.19.
Example 17: synthesis of compound 100:
Figure BDA0001937701220000203
prepared according to the synthetic method for compound 1 in example 5, except that intermediate C4 is substituted for intermediate C1; elemental analysis Structure (score)Sub-formula C54H49BO3) Theoretical values of C,85.70, H,6.53, B,1.43, test values of C,85.71, H,6.54, B,1.42, HP L C-MS, material molecular weight of 756.38, and measured molecular weight of 756.46.
Example 18: synthesis of compound 107:
Figure BDA0001937701220000211
prepared according to the method for the synthesis of compound 81 in example 15, except that intermediate G2 is substituted for intermediate C3 and starting material X1 is substituted for starting material X5; elemental analysis Structure (molecular formula C)42H28BN) theoretical value of C,90.49, H,5.06, B,1.94, N,2.51, test value of C,90.47, H,5.04, B,1.95, N,2.53, HP L C-MS material molecular weight of 557.23 and actual measured molecular weight of 557.31.
Example 19: synthesis of compound 121:
Figure BDA0001937701220000212
prepared according to the synthetic method for compound 35 in example 10, except that intermediate E2 is substituted for starting material X3; elemental analysis Structure (molecular formula C)38H26BN): theory C, 89.94; h, 5.16; b, 2.13; n, 2.76; test values are: c, 89.96; h, 5.17; b, 2.12; and N, 2.75. ESI-MS (M/z) (M +): theoretical value is 507.22, found 507.41.
Example 20: synthesis of compound 164:
Figure BDA0001937701220000213
prepared according to the synthetic method for compound 1 in example 5, except that intermediate C5 is substituted for intermediate C1; elemental analysis Structure (molecular formula C)30H21BS) theoretical value of C,84.91, H,4.99, B,2.55, S,7.55, test value of C,84.93, H,4.98, B,2.54, S,7.57, HP L C-MS, material molecular weight of 424.15, and actual measured molecular weight of 424.23.
Example 21: synthesis of compound 185:
Figure BDA0001937701220000221
prepared according to the synthetic method of the compound 9 in the example 7, except that the intermediate C6 is used instead of the raw material C1, and the raw material X6 is used instead of the raw material X1; elemental analysis Structure (molecular formula C)54H36BNO): theory C, 89.38; h, 5.00; b, 1.49; n, 1.93; test values are: c, 89.37; h, 5.01; b, 1.48; n, 1.94. ESI-MS (M/z) (M +): theoretical value is 725.29, found 725.34.
Example 22: synthesis of compound 187:
Figure BDA0001937701220000222
prepared according to the synthetic method of the compound 9 in the example 7, except that the intermediate C7 is used instead of the raw material C1, and the raw material X7 is used instead of the raw material X1; elemental analysis Structure (molecular formula C)48H30BNO2): theory C, 86.88; h, 4.56; b, 1.63; n, 2.11; test values are: c, 86.85; h, 4.57; b, 1.62; and N, 2.13. ESI-MS (M/z) (M +): theoretical value is 663.24, found 663.32.
Example 23: synthesis of compound 191:
Figure BDA0001937701220000223
Figure BDA0001937701220000231
prepared according to the synthetic method of the compound 9 in the example 7, except that the intermediate C8 is used instead of the raw material C1, and the raw material X8 is used instead of the raw material X1; elemental analysis Structure (molecular formula C)47H29BN2O2): theory C, 84.94; h, 4.40; b, 1.63; n, 4.22; o, 4.81; test values are: c, 84.954; h, 4.41; b, 1.62; n, 4.21. ESI-MS (M/z) (M +): theoretical value is 664.23, found 664.29.
Example 24: synthesis of compound 193:
Figure BDA0001937701220000232
prepared according to the method for the synthesis of compound 81 in example 15, except that intermediate I2 is substituted for intermediate C3 and starting material X9 is substituted for starting material X5; elemental analysis Structure (molecular formula C)43H29BN2) Theoretical values of C,88.36, H,5.00, B,1.85, N,4.79, test values of C,88.35, H,5.01, B,1.86, N,4.78, HP L C-MS, material molecular weight of 584.24, and actual measured molecular weight of 584.35.
Example 25: synthesis of compound 195:
Figure BDA0001937701220000233
prepared according to the method for the synthesis of compound 81 in example 15, except that intermediate I3 is substituted for intermediate C3 and starting material X10 is substituted for starting material X5; elemental analysis Structure (molecular formula C)52H29BN2) Theoretical values of C,90.17, H,4.22, B,1.56, N,4.04, test values of C,90.19, H,4.21, B,1.55, N,4.03, HP L C-MS show that the molecular weight of the material is 692.24, and the measured molecular weight is 692.29.
The compound of the invention is used in a luminescent device, can be used as an electron blocking layer material, and can also be used as a hole transport layer material. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 1:
TABLE 1
Compound (I) Tg(℃) Td(℃) △Est(eV) HOMO(ev)
Compound 1 140 403 0.13 5.69
Compound 2 144 399 0.18 5.70
Compound 9 143 404 0.12 5.74
Compound 10 147 399 0.14 5.67
Compound 21 139 403 0.10 5.67
Compound 35 143 399 0.13 5.70
Compound 41 148 400 0.15 5.71
Compound 45 144 399 0.09 5.69
Compound 64 139 400 0.16 5.71
Compound 65 148 399 0.11 5.72
Compound 81 147 404 0.16 5.66
Compound 98 144 404 0.12 5.73
Compound 100 141 404 0.15 5.68
Compound 107 140 399 0.16 5.72
Compound 121 147 405 0.17 5.67
Compound 164 140 400 0.16 5.69
Compound 185 144 402 0.15 5.67
Compound 187 139 404 0.16 5.67
Compound 191 138 399 0.14 5.69
Compound 193 140 397 0.11 5.68
Compound 195 146 397 0.12 5.68
Note that the glass transition temperature Tg was measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Chi-Daizhi Ltd., Germany), the temperature rise rate was 10 ℃/min, the thermal weight loss temperature Td was the temperature at which 1% weight loss occurs in a nitrogen atmosphere, as measured on a TGA-50H thermogravimetric analyzer, Shimadzu corporation, Japan, and the nitrogen flow rate was 20m L/min, △ Est was the difference between the singlet level and the triplet level of the material, and the fluorescence emission spectrum and the phosphorescence emission spectrum of the compound were measured, respectively, and calculated from the fluorescence emission peak and the phosphorescence emission peak (test equipment: F L S980 fluorescence spectrometer by Edinburgh Instruments, Optistat DN-V2 low temperature component by Oxford Instruments), and the highest occupied molecular orbital HOMO level was measured by an IPS3 device (vacuum photoelectron spectroscopy) to be a vacuum environment.
As can be seen from the data in the table above, the organic compound of the present invention has a high glass transition temperature and a small triplet-singlet energy level, so that the efficiency and the lifetime of an O L ED device using the compound of the present invention as a material of a light emitting layer are improved.
The application effect of the synthesized O L ED material in the device is described in detail in device examples 1-21 and comparative example 1. the device manufacturing process of device examples 2-21 of the present invention is identical to that of device example 1 of the present invention, and the same substrate material and electrode material are used, the film thickness of the electrode material is also kept consistent, except that the doped material of the light emitting layer in the device is replaced, the device structure of each example is shown in Table 2, and the performance test results of the device obtained in each example are shown in Table 3.
Device example 1
As shown in fig. 1, an electroluminescent device is prepared by a) cleaning an ITO anode layer 2 on a transparent substrate layer 1, ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone, and ethanol for 15 minutes, respectively, and then treating the cleaned layer in a plasma cleaner for 2 minutes, b) evaporating a hole injection layer material HAT-CN having a thickness of 10nm as a hole injection layer 3 on the ITO anode layer 2 by vacuum evaporation, c) evaporating a hole transport material compound HT-1 having a thickness of 60nm as a hole transport layer 4 on the hole injection layer 3, d) evaporating an electron blocking material EB-1 having a thickness of 20nm as an electron blocking layer 5 on the hole transport layer 4 by vacuum evaporation, e) evaporating a light emitting layer 6 on the electron blocking layer 5 with a host material of GH-2 and GH-1, a dopant material compound 1, a compound GH-2, a compound-1, a compound GH-1, a compound 3, and a compound 3 having a mass ratio of 45:45:10, a thickness of 30nm, f) on the electron blocking layer 6, an electron blocking layer 24 nm as a hole transport layer, and an electron transport layer 3 as a cathode transport layer 3, and an electron transport layer 3 as an electron transport layer 3, and an electron transport layer 3 as a thickness measured by vacuum evaporation, and an electron transport layer 3, and an electron transport layer as a cathode transport layer 3, wherein the electron transport layer 3 is formed by vacuum evaporation, and an electron transport layer having a thickness of 635, and an electron transport efficiency measured as a thickness of 100nm, and an electron transport efficiency measured as a thickness of a cathode layer shown in the following steps:
Figure BDA0001937701220000251
TABLE 2
Figure BDA0001937701220000261
Figure BDA0001937701220000271
The inspection data of the obtained electroluminescent device are shown in Table 3.
TABLE 3
Figure BDA0001937701220000272
Note that the life test system is an O L ED device life tester, which is commonly studied by the owner of the present invention and the university of shanghai.
From the results of table 3, it can be seen that the organic compound of the present invention can be applied to the fabrication of O L ED light emitting devices, and compared with the comparative example, the organic compound has a greater improvement in efficiency and lifetime than the known O L ED material, and particularly, the organic compound has a greater improvement in the lifetime of the device.
Further, the efficiency of the O L ED device prepared by the material is stable when the device works at low temperature, and the results of efficiency tests conducted on device examples 3, 8 and 20 and device comparative example 1 at the temperature range of-10 to 80 ℃ are shown in Table 4 and FIG. 2.
TABLE 4
Figure BDA0001937701220000281
As can be seen from the data in table 4 and fig. 2, device examples 3, 8, and 20 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. An organic electroluminescent material containing boron, characterized in that the structure of the compound is shown as the general formula (1):
Figure FDA0001937701210000011
in the general formula (1), X1、X2、X3Independently represent a sulfur atom, an oxygen atom,
Figure FDA0001937701210000012
N(R5)、B(R6) Or C (R)7)(R8)，X3May also represent a single bond; wherein R is7And R8Can be connected with each other to form a ring;
a. b and c are respectively and independently 0 or 1;
R1-R4each independently represents a hydrogen atom, a substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C2-20Alkenyl of (a), substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, C6-30Aryl or 5 to 30 membered heteroaryl substituted amino, substituted or unsubstituted styryl; and R is1And R2、R3And R4Can be connected with each other to form a ring;
z is1-Z5Each independently represents a nitrogen atom or C-Ri(ii) a Wherein i represents 1, 2, 3 or 4;
the R is5-R8Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered containing one or more heteroatomsA heteroaryl group;
the R isiEach independently represents a hydrogen atom, a cyano group, deuterium, a halogen atom, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms; and at least one RiNot represented as a hydrogen atom;
the substituents of said substitutable groups are optionally selected from protium, cyano, halogen, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The boron-containing organic electroluminescent material according to claim 1, wherein R isiEach independently represents a hydrogen atom, deuterium, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted azabenzophenanthryl group, a structure represented by a general formula (2), a general formula (3) or a general formula (4);
Figure FDA0001937701210000021
z represents a nitrogen atom or a carbon atom; z at the attachment site is represented as a carbon atom;
the L, L1、L2Each independently represents a single bond, a substituted or substituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazole groupA substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted pyrenylene group, or a substituted or unsubstituted benzophenanthrenylene group;
s, t and n are respectively and independently 0, 1 or 2;
the R isa、Rb、RcEach independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms; ra、Rb、RcThe connection mode with the general formula (2) or the general formula (3) includes two modes of ring merging and substitution;
each A, B independently represents a substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms;
said X4、X5、X6Each independently represents a single bond, -O-, -S-, -C (R)16)(R17) -or-N (R)18) -, and X4、X5Not simultaneously represent a single bond; r16And R17Can be connected with each other to form a ring;
the R is16-R18Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms;
the substituent of the substitutable group is selected from deuterium, cyano, halogen and C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
3. The boron-containing organic electroluminescent material according to claim 1, wherein R isa、Rb、RcRespectively independent earth surfaceShown as a hydrogen atom, deuterium, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted azacarbazolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted dibenzofuryl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted benzopyrolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted benzindenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted phenyl group, Substituted or unsubstituted azabenzophenanthryl;
a, B are respectively and independently represented by substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted anthryl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzophenanthryl, and substituted or unsubstituted azabenzophenanthryl;
the R is1-R4Each independently represents one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenoxy group, a substituted or unsubstituted phenyl group, a methoxy group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenylamino group, and a substituted or unsubstituted vinyl group;
the R is5-R8、R16-R18Each independently represents one of methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, terphenyl, pyridyl or furyl;
the substituent of the substitutable group is one or more selected from deuterium, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group or furyl group.
4. The boron-containing organic electroluminescent material according to claim 1, wherein the general formula (1) can be represented by a structure represented by a general formula (5), a general formula (6), a general formula (7), a general formula (9), a general formula (10) or a general formula (11);
Figure FDA0001937701210000031
the R is19、R20Each independently represents one of phenyl, pyridyl, naphthyl, naphthyridinyl, pyridyl, biphenyl, terphenyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl.
5. The boron-containing organic electroluminescent material according to claim 1, wherein R is1And R2、R3And R4At least one of which is looped.
6. The boron-containing organic electroluminescent material of claim 1, wherein at least one of a, b and c is 1.
7. The organic electroluminescent material according to claim 1, wherein the specific structure of the general formula (1) is:
Figure FDA0001937701210000041
Figure FDA0001937701210000051
Figure FDA0001937701210000061
Figure FDA0001937701210000071
one kind of (1).
8. An organic electroluminescent device comprising at least one functional layer comprising the boron-containing organic electroluminescent material according to any one of claims 1 to 7.
9. The organic electroluminescent device according to claim 8, wherein the functional layer comprises a light-emitting layer, and wherein the light-emitting layer comprises the boron-containing organic electroluminescent material according to any one of claims 1 to 7.
10. A lighting or display element comprising the organic electroluminescent device according to any one of claims 9 or 8.
CN201910012073.5A 2019-01-07 2019-01-07 Organic electroluminescent material containing boron and application thereof in organic electroluminescent device Withdrawn CN111410952A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574543A (en) * 2019-02-18 2020-08-25 江苏三月科技股份有限公司 Organic compound containing boron and application thereof in organic electroluminescent device
CN113583030A (en) * 2020-09-02 2021-11-02 广东聚华印刷显示技术有限公司 Condensed-ring aromatic hydrocarbon organic compound, composition and light-emitting device
CN114075225A (en) * 2020-08-14 2022-02-22 广州华睿光电材料有限公司 Boron-containing organic compounds and uses thereof
CN114685465A (en) * 2020-12-29 2022-07-01 江苏三月科技股份有限公司 Organic compound containing ketone and organic electroluminescent device containing organic compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110573516A (en) * 2017-07-07 2019-12-13 株式会社Lg化学 Novel compound and organic light emitting device comprising same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110573516A (en) * 2017-07-07 2019-12-13 株式会社Lg化学 Novel compound and organic light emitting device comprising same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUMIYA MIYAMOTO等: "Synthesis of Boron-Doped Polycyclic Aromatic Hydrocarbons by Tandem Intramolecular Electrophilic Arene Borylation", 《ORG. LETT.》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574543A (en) * 2019-02-18 2020-08-25 江苏三月科技股份有限公司 Organic compound containing boron and application thereof in organic electroluminescent device
CN114075225A (en) * 2020-08-14 2022-02-22 广州华睿光电材料有限公司 Boron-containing organic compounds and uses thereof
CN114075225B (en) * 2020-08-14 2024-02-27 广州华睿光电材料有限公司 Boron-containing organic compounds and uses thereof
CN113583030A (en) * 2020-09-02 2021-11-02 广东聚华印刷显示技术有限公司 Condensed-ring aromatic hydrocarbon organic compound, composition and light-emitting device
CN114685465A (en) * 2020-12-29 2022-07-01 江苏三月科技股份有限公司 Organic compound containing ketone and organic electroluminescent device containing organic compound
CN114685465B (en) * 2020-12-29 2024-04-02 江苏三月科技股份有限公司 Ketone-containing organic compound and organic electroluminescent device comprising same

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