CN110577545B

CN110577545B - Triarylamine compound and application thereof in organic electroluminescent device

Info

Publication number: CN110577545B
Application number: CN201810580506.2A
Authority: CN
Inventors: 李崇; 蔡啸; 张兆超; 赵四杰; 徐浩杰
Original assignee: Jiangsu Sunera Technology Co Ltd
Current assignee: Jiangsu Sunera Technology Co Ltd
Priority date: 2018-06-07
Filing date: 2018-06-07
Publication date: 2021-04-16
Anticipated expiration: 2038-06-07
Also published as: CN110577545A

Abstract

The invention discloses a triarylamine-containing compound and application thereof in an organic electroluminescent device, wherein the compound contains a triarylamine structure and has stronger electron-rich property, and after the compound is connected with a carbazole derivative long-chain branched structure, the molecules are not easy to crystallize and aggregate, and the compound has the characteristics of good film-forming property; the compound has rich electrons, the branched chain is an electron-donating group, and because the electron-donating capability of the group is different, the HOMO energy levels of the material are different, and the material can be used as materials of different functional layers; in addition, the compound has high triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.

Description

Triarylamine compound and application thereof in organic electroluminescent device

Technical Field

The invention relates to the technical field of semiconductors, in particular to a compound containing a triarylamine structure and application thereof in an organic electroluminescent device.

Background

The Organic Light Emission Diodes (OLED) 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 OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.

At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance. The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials. In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.

The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a triarylamine compound and application thereof in an organic electroluminescent device. The compound contains a triarylamine structure and has strong electron-rich performance, so that the hole mobility is favorably improved, and meanwhile, the nitrogen atom in the triarylamine structure is connected with three different rigid groups, so that the compound also has high glass transition temperature and molecular thermal stability. In addition, the compound also contains carbazole derivatives, and the carbazole derivatives have different electron donating capability groups by connecting various groups (different ring merging modes) on carbazole benzene rings, so that the HOMO and LUMO energy levels of the compound can be adjusted to achieve the appropriate HOMO and LUMO energy levels required by the device, and after the compound is applied to the manufacturing of an OLED device, the luminous efficiency of the device can be remarkably improved, and the service life of the OLED device can be remarkably prolonged.

The technical scheme of the invention is as follows:

a triarylamine compound has a structure shown in a general formula (1):

in the general formula (1), X₁Represented by-O-, -S-, -C (R)₄)(R₅)-、-N(R₆) -or-Si (R)₇)(R₈)-；

R₄～R₈Is represented as C_1-10Alkyl, substituted or unsubstituted C_6-60One of aryl and substituted or unsubstituted 5-to 60-membered heteroaryl containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; r₄And R₅、R₇And R₈Can be bonded to each other to form a ring;

a represents the

number

0, 1, 2, 3 or 4;

ar represents a hydrogen atom, substituted or unsubstituted C_6-60One of aryl and substituted or unsubstituted 5-to 60-membered heteroaryl containing one or more heteroatoms selected from nitrogen, oxygen or sulfur;

said L₁、L₂Each independently represents substituted or unsubstituted C_6-60One of arylene, 5-to 60-membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is selected from nitrogen, oxygen or sulfur; l is₁And L₂The same or different; l is₁May also represent a single bond;

Z₁～Z₈each independently represents an N atom or C-R₉；

R₂、R₃Are each independently of Z₁～Z₈In the case of a bond and₁～Z₈is represented as C;

R₁、R₉respectively represent hydrogen atom, protium atom, deuterium atom, tritium atom, cyano group, halogen, C_1-10Alkyl, substituted or unsubstituted C_6-60One of aryl and 5-60 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted, the heteroatomIs selected from nitrogen, oxygen or sulfur;

the R is₂、R₃Is represented by a hydrogen atom, a structure represented by the general formula (3) or the general formula (4), and R₂、R₃Not hydrogen at the same time;

wherein, X₂、X₃Each independently represents a single bond, -O-, -S-, -C (R)₁₀)(R₁₁)-、-N(R₁₂) -or-Si (R)₁₃)(R₁₄)-；X₂、X₃Are the same or different, and X₂、X₃Not being a single bond at the same time;

R₁₀～R₁₄is represented as C_1-10Alkyl, substituted or unsubstituted C_6-60One of aryl and substituted or unsubstituted 5-to 60-membered heteroaryl containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; r₁₀And R₁₁、R₁₃And R₁₄Can be bonded to each other to form a ring;

Z₉～Z₁₂each independently represents an N atom or C-R₁₅；

R₁₅Represented by hydrogen atom, protium atom, deuterium atom, tritium atom, cyano group, halogen, C1-10 alkyl group, substituted or unsubstituted C_6-60One of aryl and substituted or unsubstituted 5-to 60-membered heteroaryl containing one or more heteroatoms selected from nitrogen, oxygen or sulfur;

the general formula (3) or the general formula (4) is connected with two adjacent connecting sites in the general formula (1) in a ring-by-ring mode; when the general formula (3) or the general formula (4) is bonded to the general formula (1), the overlapping bonding site is represented by a carbon atom;

the substituent is halogen, cyano, C_1-20Alkyl or C_6-20And (4) an aryl group.

Preferably, Ar represents a hydrogen atom, a cyano group, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group;

said L₁、L₂Are each independently represented by C_1-10Alkyl-substituted or unsubstituted phenylene radicals, C_1-10Alkyl-substituted or unsubstituted naphthylene, C_1-10Alkyl-substituted or unsubstituted biphenylene, C_1-10An alkyl substituted or unsubstituted pyridylene group; l is₁And L₂The same or different; l is₁May also represent a single bond;

the R is₁Is represented as C_1-10Alkyl-substituted or unsubstituted phenyl, C_1-10Alkyl-substituted or unsubstituted naphthyl, C_1-10Alkyl-substituted or unsubstituted biphenyl, C_1-10Alkyl-substituted or unsubstituted pyridyl, C_1-10Alkyl substituted or unsubstituted carbazolyl, C_1-10Alkyl substituted or unsubstituted dibenzofuranyl or C_1-10Alkyl substituted or unsubstituted 9, 9-dimethylfluorenyl;

the R is₁、R₉、R₁₅Each independently represents a hydrogen atom, a cyano group, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group.

The R is₄～R₈、R₁₀～R₁₄Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl.

Preferably, the compound is selected from any one of structures represented by general formula (II-1) to general formula (II-3):

preferably, the compound is selected from any one of structures represented by general formulae (III-1) to (III-3):

preferably, the compound is selected from any one of structures shown in general formula (IV-1) to general formula (IV-3):

when R is in the specification₂Is of the general formula (3), and X₃In the case of a single bond, the bond may be classified into the following three types, for example, the mode of bonding to the general formula (1):

1、R₂with general formula (1) through Z₁-Z₂Bonding mode (a)

2、R₂With general formula (1) through Z₂-Z₃The bonding mode can be (b)

3、R₂With general formula (1) through Z₃-Z₄The bonding mode can be (c)

In one embodiment, the compounds of the present invention are of the general formula (M-1):

in the formula (M-1), a, Z₁-Z₁₂、L₁、L₂、R₁X has the meaning listed in the following table 1, and represents a connecting site, and when the X is connected, only two adjacent sites can be taken; when R2 is bonded to the general formula (M-1), the bonding site Z₁、Z₂、Z₃Or Z₄Represented as a carbon atom; and R is₂Is composed of

R₃Is a hydrogen atom;

TABLE 1

Note:

represents connection with other portions, the same as follows.

Compounds 13-24, which in turn have the same structure as compounds 1-12, except that L₂Is shown as

Compounds 25-36, which in turn have the same structure as compounds 1-12, except that L₂Is shown as

Compounds 37-48, which in turn have the same structure as compounds 1-12, except that L₂Is shown as

Compounds 49-60, which in turn have the same structure as compounds 1-12, except that L₂Is shown as

Compounds 61-120, which in turn have the same structure as compounds 1-60, except that R is₂From the original

Is converted into

Wherein X₂Is O, and X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

the compound 121-180, which in turn has the same structure as the compounds 1-60, except that R is₂From the original

Is converted into

Wherein X₂Is C (CH)₃)₂And X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

the compound 181-240, which in turn has the same structure as the compounds 1-60, except that R is₂From the original

Is converted into

Wherein X₂Is S, and X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄Are bonded in the manner ofThe above (a), (b) or (c);

the compound 241-300, which in turn has the same structure as the compounds 1-60, except that R is₂From the original

Is converted into

Wherein X₂Is a phenyl-substituted nitrogen atom, and X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

compound 301-360, which in turn has the same structure as compounds 1-60, except that R₂From the original

Is converted into

Wherein X₂Is O, and X₃Is O, and R₂(ii) by bonding of Z1-Z2, Z2-Z3 or Z3-Z4 as described above for (a), (b) or (c), respectively;

compound 361-420 having the same structure as compounds 1-60 in that order except that R₂From the original

Is converted into

Wherein X₂Is O, and X₃Is C (CH)₃)₂And R is₂(ii) by bonding of Z1-Z2, Z2-Z3 or Z3-Z4 as described above for (a), (b) or (c), respectively;

the compound 421-840, which in turn has the same structure as the compounds 1-420, except that Z5 is an N atom, except that the fused ring position represents carbonAtom, the rest Z₁-Z₁₂Represents CH;

compound 841-1260, which in turn has the same structure as compounds 1-420, except that Z6 is an N atom, the remainder of Z being Z, except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

the compound 1261-1680, which in turn has the same structure as the compounds 1-420, except that Z7 is an N atom, the exception of the fused ring position representing a carbon atom, the remaining Z₁-Z₁₂Represents CH;

the compound 1681-2100, which in turn has the same structure as the compounds 1-420, except that Z8 is an N atom, the remainder of Z, except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

compound 2101-2520 which in turn has the same structure as compounds 1 to 420, with the difference that Z9 is an N atom, the remainder of Z being Z atoms except for the fused ring position which represents a carbon atom₁-Z₁₂Represents CH;

compound 2521-2940 having the same structure in this order as compounds 1 to 420, except that Z10 is an N atom, except that the fused ring position represents a carbon atom, and the remaining Z is₁-Z₁₂Represents CH;

compound 2941-3360, which in turn has the same structure as compounds 1-420, except that Z11 is an N atom, the remainder of Z being Z atom except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

compound 3361-3780, which in turn has the same structure as compounds 1-420, except that Z12 is an N atom, the remainder of Z, except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

compound 3781-4200, which in turn has the same structure as compounds 1-420, except that Z6 and Z8 are both N atoms, the remainder of Z, except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

compound 4201-4620, which in turn has the same structure as compounds 1 to 420, except that Z10 and Z12 are both N atoms, the remainder of Z, except that the fused ring position represents a carbon atom₁-Z₁₂Represents CH;

compound 4621-9240, which in turn has the same structure as compounds 1-4620, except that,

the attachment site of (a) is P2;

compound 9241-13860, which in turn has the same structure as compounds 1-4620, except that,

the attachment site of (a) is P3;

compound 13861-18480, which in turn has the same structure as Compound 1-4620, except that,

the attachment site of (a) is P4;

compound 18481-36960, which in turn has the same structure as compounds 1-18480, except that X1 represents a dimethyl-substituted carbon atom;

compounds 36961-73920, in turn, having the same structures as compounds 1-36960, except that the original R3 is replaced by a hydrogen atom

And R is₃To the linking position of the formula (M-1) and R₂The same as the linking position of the general formula (M-1);

compound 73921-147840, which in turn has the same structure as compound 1-36960, except that the original R3 represents a hydrogen atom to be converted into

Wherein X₂Is O, and X₃Is a single bond, and R₃To the linking position of the formula (M-1) and R₂The same as the linking position of the general formula (M-1);

in another embodiment, the compounds of the present invention are of the general formula (M-2):

in the formula (M-2), a, Z₁-Z₁₂、L₁、L₂、R₁X has the following meanings listed in Table 2, and represents a connecting site, and when connected, only two adjacent sites can be taken; when R2 is bonded to the general formula (M-1), the bonding site Z₁、Z₂、Z₃Or Z₄Represented as a carbon atom; and R is₂Is represented by the general formula (3), R3 is a hydrogen atom;

TABLE 2

The compound 13 '-24', which in turn has the same structure as the compound 1 '-12', except that L₂Is shown as

Compounds 25 '-36', which in turn have the same structure as compounds 1 '-12', except that L₂Is shown as

Compounds 37 '-48', which in turn have the same structure as compounds 1 '-12', except that L₂Is shown as

Compounds 49 '-60', which in turn have the same structure as compounds 1 '-12', except that L₂Is shown as

Compounds 61 '-120', which in turn have the same structure as compounds 1 '-60', except that R is₂From the original

Is converted into

compounds 121 '-180', which in turn have the same structure as compounds 1 '-60', except that R₂From the original

Is converted into

compounds 181 '-240', in turn, have the same structure as compounds 1 '-60', except that R is₂From the original

Is converted into

Wherein X₂Is S, and X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

compounds 241 '-300', which in turn have the same structure as compounds 1 '-60', except that R₂From the original

Is converted into

compounds 301 '-360', which in turn have the same structure as compounds 1 '-60', except that R₂From the original

Is converted into

Wherein X₂Is O, and X₃Is O, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

compounds 361 '-420', which in turn have the same structure as compounds 1 '-60', except that R is₂From the original

Is converted into

Wherein X₂Is O, and X₃Is C (CH)₃)₂And R is₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄Respectively, are bonded in a manner of(ii) the above-mentioned (a), (b) or (c);

compounds 421 '-840', which in turn have the same structure as Compounds 1 '-420', except that Z₅Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compounds 841 '-1260', which in turn have the same structure as Compounds 1 '-420', except that Z₆Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 1261 '-1680', which in turn has the same structure as compound 1 '-420', except that Z₇Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 1681 '-2100', which in turn has the same structure as compound 1 '-420', except that Z₈Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2101 '-2520', which in turn has the same structure as compound 1 '-420', except that Z₉Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2521 '-2940', which in turn has the same structure as compound 1 '-420', except that Z has the same structure₁₀Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2941 '-3360', which in turn has the same structure as compound 1 '-420', except that Z₁₁Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 3361 '-3780', which in turn has the same structure as compound 1 '-420', except that Z is₁₂Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 3781 '-4200'Which in turn have the same structure as compound 1 '-420', except that Z is₆、Z₈Are all N atoms except the ring-merging position representing a carbon atom, the remainder Z₁-Z₁₂Represents CH;

compound 4201 '-4620', which in turn has the same structure as compound 1 '-420', with the difference that Z is₁₀、Z₁₂Are all N atoms except the ring-merging position representing a carbon atom, the remainder Z₁-Z₁₂Represents CH;

compound 4621 '-9240', which in turn has the same structure as Compound 1 '-4620', except that,

the attachment site of (a) is P2;

compound 9241 '-13860', which in turn has the same structure as compound 1 '-4620', except that,

the attachment site of (a) is P3;

compound 13861 '-18480', which in turn has the same structure as compound 1 '-4620', except that,

the attachment site of (a) is P4;

compound 18481 '-36960', which in turn has the same structure as compound 1 '-18480', except that X₁Represented as a dimethyl-substituted carbon atom;

compound 36961 '-73920' having the same structure as compound 1 '-36960' in that order except that R3 represents a hydrogen atom

compound 73921 '-147840', which isHas the same structure as that of compound 1 '-36960' except that the original R3 represents a hydrogen atom and is converted into

the compound of the present invention is a compound represented by the general formula (M-3);

in the formula (M-3), a, Z₁-Z₁₂、L₁、L₂、R₁X has the meaning listed in the following table 1, and represents a connecting site, and when the X is connected, only two adjacent sites can be taken; when R2 is bonded to the general formula (M-1), the bonding site Z₁、Z₂、Z₃Or Z₄Represented as a carbon atom; and R is₂Is composed of

General formula (3), R3 is a hydrogen atom;

TABLE 3

Compound 13 "-24", which in turn has the same structure as Compound 1 "-12", except that L₂Is shown as

Compounds 25 "-36", which in turn have the same structure as compounds 1 "-12",except that L is₂Is shown as

Compounds 37 "-48", which in turn have the same structure as Compounds 1 "-12", except that L₂Is shown as

Compound 49 '-60' which in turn has the same structure as compound 1 '-12' except that L₂Is shown as

Compounds 61 "-120", having in sequence the same structure as Compounds 1 "-60", except that R is₂From the original

Is converted into

compounds 121 "-180", having in sequence the same structures as Compounds 1 "-60", except that R is₂From the original

Is converted into

Wherein X₂Is C (CH)₃)₂And X₃Is a single bond, and R₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄Bonding method of(ii) as described above for (a), (b) or (c), respectively;

compounds 181 '-240' which in turn have the same structures as compounds 1 '-60' except that R is₂From the original

Is converted into

compounds 241 "-300", having in sequence the same structures as compounds 1 "-60", except that R is₂From the original

Is converted into

compound 301 "-360", which in turn has the same structure as Compound 1 "-60", except that R is₂From the original

Is converted into

compounds 361 "-420", which in turn have the same structures as compounds 1 "-60", except that R is₂From the original

Is converted into

Wherein X₂Is O, and X₃Is C (CH)₃)₂And R is₂Through Z₁-Z₂、Z₂-Z₃Or Z₃-Z₄The bonding modes of (a), (b) or (c) described above;

compound 421 "-840", which in turn has the same structure as compound 1 "-420", except that Z is₅Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 841 "-1260", which in turn has the same structure as Compound 1 "-420", except that Z is₆Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 1261 "-1680", which in turn has the same structure as Compound 1 "-420", except that Z is₇Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 1681 "-2100", which in turn has the same structure as compound 1 "-420", except that Z has the same structure₈Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2101 "-2520", which in turn has the same structure as Compound 1 "-420", except that Z₉Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2521 "-2940", having in turn the same structure as compound 1 "-420", except that Z is₁₀Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 2941 "-3360", which in turn has the same structure as compound 1 "-420", except that Z has the same structure₁₁Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 3361 "-3780", having in turn the same structure as compound 1 "-420", except that Z is₁₂Is a N atom, the remainder Z being carbon atoms except for the ring-merging position₁-Z₁₂Represents CH;

compound 3781 '-4200' which in turn has the same structure as Compound 1 '-420' except that Z is₆、Z₈Are all N atoms except the ring-merging position representing a carbon atom, the remainder Z₁-Z₁₂Represents CH;

compound 4201 "-4620", which in turn has the same structure as compound 1 "-420", with the difference that Z is₁₀、Z₁₂Are all N atoms except the ring-merging position representing a carbon atom, the remainder Z₁-Z₁₂Represents CH;

compound 4621 "-9240", which in turn has the same structure as compound 1 "-4620", except that,

the attachment site of (a) is P2;

compound 9241 "-13860", which in turn has the same structure as compound 1 "-4620", except that,

the attachment site of (a) is P3;

compound 13861 "-18480", which in turn has the same structure as compound 1 "-4620", except that,

the attachment site of (a) is P4;

compound 18481 "-36960", which in turn has the same structure as compound 1 "-18480", except that X1 represents a dimethyl-substituted carbon atom;

compound 36961 '-73920' having the same structure as Compound 1 '-36960' in that order, except that R3 represents a hydrogen atom

compound 73921 "-147840", which in turn has the same structure as Compound 1 "-36960", except that R is replaced by the original one₃Expressed as hydrogen atoms into

the triarylamine compound preferably has the following structure, but is not limited thereto:

any one of the above.

A preparation method of the triarylamine compound relates to a reaction formula as follows:

the specific reaction process of the above reaction equation is:

(1) dissolving the intermediate G and the raw material D in toluene; the molar ratio of the intermediate G to the raw material D is 1: 1.0-1.5;

(2) adding Pd (PPh) into the reaction system in the step (1)₃)₄Mixing with water and ethanol (volume ratio of 1:1) solution of sodium carbonate to obtain mixed solution; the Pd (PPh)₃)₄The molar ratio of the intermediate G to the sodium carbonate is 0.005-0.01: 1, the molar ratio of the sodium carbonate to the intermediate G is 1.5-3.0: 1, and the volume ratio of the toluene to the water to the ethanol is 2:1: 1;

(3) under the protection of inert gas, reacting the mixed solution obtained in the step (2) at the temperature of 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering the reaction solution, performing rotary evaporation on the filtrate until no solvent exists, and passing through a neutral silica gel column to obtain a target product M;

the application of the triarylamine compound is used for preparing an organic electroluminescent device.

An organic electroluminescent device comprises at least one functional layer containing the triarylamine compound.

The triarylamine compound is used as a hole transport layer or an electron barrier layer material for manufacturing an organic electroluminescent device.

A lighting or display element comprising said organic electroluminescent device.

The beneficial technical effects of the invention are as follows:

the compound takes triarylamines as a framework and is connected with a carbazole derivative long branched chain structure, because the electron donating capability of branched chain groups is different, the HOMO energy level of the whole structure of the compound can be freely adjusted, and the compound with shallow HOMO energy level can be used as a hole transport layer material; materials with deep HOMO levels can be used as electron blocking layer materials.

In addition, the triarylamine group is a double-property group, and the branched chain is a long-chain structure, so that the symmetry of the molecular structure is destroyed, and the aggregation effect among molecules is avoided; the branched chain group of the compound also has strong rigidity, so that molecules are not easy to aggregate and crystallize, and the compound has good film forming property, high glass transition temperature and thermal stability.

In addition, the compound has high triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.

Drawings

FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;

wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a luminescent layer, 7 is a hole blocking/electron transport layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.

Fig. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a device of a comparative example.

FIG. 3 is a graph showing reverse voltage leakage current test performed on devices manufactured in example 1 of the device of the present invention and comparative example 1 of the device.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and examples.

Example 1, synthesis of intermediate G:

(1) weighing raw material I and raw material J, Pd (PPh) under nitrogen atmosphere₃)₄Stirring and mixing toluene and ethanol, dissolving sodium carbonate in water, then adding a sodium carbonate aqueous solution into a reaction system, heating to 100-120 ℃, carrying out reflux reaction for 10-24 hours, naturally cooling to room temperature after the reaction is finished, filtering, layering filtrate, taking an organic phase, carrying out reduced pressure rotary evaporation, and purifying through a neutral silica gel column to obtain an intermediate K; the molar ratio of the raw material I to the raw material J is 1.2-2: 1, the molar ratio of sodium carbonate to the raw material I is 2.0-3.0: 1, and Pd (PPh)₃)₄The molar ratio of the raw material I to the raw material I is 0.01-0.02: 1, and the volume ratio of the toluene, the ethanol and the water is 2:1: 1;

(2) weighing the intermediate K, dissolving the intermediate K in o-dichlorobenzene, adding triphenylphosphine, reacting at 180-200 ℃ for 12-24 hours, cooling to room temperature after the reaction is finished, filtering, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate F; wherein the volume of 0.01mol of o-dichlorobenzene required by the intermediate K is 100-200 ml; intermediates K and PPh₃The molar ratio of (A) to (B) is 1: 0.01-0.05;

(3) weighing raw material A and raw material B, dissolving in toluene under nitrogen atmosphere, and dissolving Pd₂(dba)₃Adding tri-tert-butylphosphine, stirring the mixture, adding sodium tert-butoxide, heating and refluxing the mixed solution of the reactants at the reaction temperature of 95-120 ℃ for 10-24 h, cooling to room temperature after the reaction is finished, filtering the reaction solution, performing rotary evaporation on the filtrate until no solvent exists, and passing through a neutral silica gel column to obtain an intermediate E; the molar ratio of the raw material A to the raw material B is 1: 1-2, and the Pd₂(dba)₃The molar ratio of the tert-butyl phosphine to the raw material A is 0.005-0.02: 1, the molar ratio of the tri-tert-butyl phosphine to the raw material A is 0.005-0.02: 1, and the molar ratio of the sodium tert-butoxide to the raw material A is 1.5-3.0: 1;

(4) weighing intermediate E and raw material C, dissolving in toluene under nitrogen atmosphere, and dissolving Pd₂(dba)₃Adding tri-tert-butylphosphine, stirring the mixture, adding sodium tert-butoxide, heating and refluxing the mixed solution of the reactants at the reaction temperature of 95-120 ℃ for 10-24 h, cooling to room temperature after the reaction is finished, filtering the reaction solution, performing rotary evaporation on the filtrate until no solvent exists, and passing through a neutral silica gel column to obtain an intermediate S; wherein the molar ratio of the intermediate E to the raw material S is 1: 1.0-2.0, and the raw material Pd₂(dba)₃The molar ratio of the tert-butyl phosphine to the intermediate E is 0.005-0.01: 1, the molar ratio of the tri-tert-butyl phosphine to the intermediate E is 0.005-0.02: 1, and the molar ratio of the sodium tert-butoxide to the intermediate E is 1.5-3.0: 1;

(5) weighing intermediate S and intermediate F, dissolving in toluene under nitrogen atmosphere, and dissolving Pd₂(dba)₃Adding tri-tert-butylphosphine, stirring the mixture, adding sodium tert-butoxide, heating and refluxing the mixed solution of the reactants at the reaction temperature of 95-120 ℃ for 10-24 h, cooling to room temperature after the reaction is finished, filtering the reaction solution, performing rotary evaporation on the filtrate until no solvent exists, and passing through a neutral silica gel column to obtain an intermediate G; wherein the molar ratio of the intermediate S to the intermediate F is 1: 1-2, and the Pd is₂(dba)₃The molar ratio of the sodium tert-butoxide to the intermediate S is 0.005-0.02: 1, the molar ratio of the tri-tert-butylphosphine to the intermediate S is 0.005-0.02: 1, and the molar ratio of the sodium tert-butoxide to the intermediate S is 1.5-3.0: 1;

synthesis example of intermediate G7:

(1) adding 0.01mol of raw material A1, 0.012mol of raw material B1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide and 1 multiplied by 10^-4mol Pd₂(dba)₃，1×10^-4Heating and refluxing the tri-tert-butylphosphine for 24 hours, sampling a sample, and displaying that no raw material A1 remains and the reaction is complete; naturally cooling to room temperature, filtering, and collecting filtratePerforming reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate E3, wherein the HPLC purity is 98.5%, and the yield is 62.4%;

(2) adding 0.01mol of intermediate E3, 0.012mol of raw material C1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide, 1 multiplied by 10^-4mol Pd₂(dba)₃，1×10^-4Heating and refluxing the mol of tri-tert-butylphosphine for 24 hours, and sampling a sample, wherein no intermediate E3 is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate S7, wherein the HPLC purity is 98.9%, and the yield is 65.7%;

(3) adding 0.01mol of intermediate S7, 0.012mol of intermediate F4 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.03mol of sodium tert-butoxide and 1 multiplied by 10^-4mol Pd₂(dba)₃，1×10^-4Heating and refluxing the mol of tri-tert-butylphosphine for 24 hours, and sampling a sample, wherein no intermediate S7 remains and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate G7, wherein the HPLC purity is 99.1% and the yield is 70.2%;

elemental analysis Structure (molecular formula C)₄₅H₃₃ClN₂): theoretical value C, 84.82; h, 5.22; cl, 5.56; n, 4.40; test values are: c, 84.83; h, 5.20; cl, 5.54; n, 4.43. ESI-MS (M/z) (M)⁺): theoretical value is 636.23, found 636.41.

Synthesis example of intermediate G11:

(1) adding 0.01mol of raw material I3, 0.012mol of raw materials J3 and 1X 10 into a 250ml three-mouth bottle under the protection of nitrogen^-4molPd(PPh₃)₄100mL of toluene and 50mL of ethanol are stirred and mixed, 0.03mol of sodium carbonate is dissolved in 50mL of water, then the sodium carbonate aqueous solution is added into the reaction system and heated to 110 ℃,refluxing for 24 hours, sampling a sample, and indicating that no raw material I3 remains and the reaction is complete; naturally cooling to room temperature, filtering, layering the filtrate, taking an organic phase, carrying out reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate K7, wherein the HPLC purity is 98.6%, and the yield is 76.5%;

(2) in a 250ml three-necked flask, 0.01mol of the intermediate K7 prepared is dissolved in 100ml of o-dichlorobenzene under nitrogen protection, and then 0.02mol of triphenylphosphine (PPh) is added₃) The mixture was heated to 200 ℃ for 15 hours and the reaction was observed by TLC until the reaction was complete. Naturally cooling to room temperature, filtering, distilling the filtrate under reduced pressure (-0.09MPa, 85 deg.C) until no fraction is produced, and purifying the obtained substance with silica gel column to obtain intermediate F7 with purity of 99.3% and yield of 67.4%.

(3) Adding 0.01mol of intermediate E2, 0.012mol of raw material C1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide, 1 multiplied by 10^-4mol Pd₂(dba)₃，1×10^-4Heating and refluxing the mol of tri-tert-butylphosphine for 24 hours, and sampling a sample, wherein no intermediate E2 is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate S11, wherein the HPLC purity is 98.9%, and the yield is 63.5%;

(4) adding 0.01mol of intermediate S11, 0.012mol of intermediate F7 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.03mol of sodium tert-butoxide and 1 multiplied by 10^-4mol Pd₂(dba)₃，1×10^-4Heating and refluxing the mol of tri-tert-butylphosphine for 24 hours, and sampling a sample, wherein no intermediate S11 remains and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and purifying by a neutral silica gel column to obtain an intermediate G11, wherein the HPLC purity is 98.8% and the yield is 58.7%;

elemental analysis Structure (molecular formula C)₄₀H₂₅ClN₄O): theoretical value C, 78.36; h, 4.11; b, 5.78; n, 9.14; o, 2.61; test values are: c, 78.37; h, 4.13; b, 5.75; n, 9.15; o, 2.60. ESI-MS (M/z) (M)⁺): theoretical value is 612.17, found 612.28.

Intermediate G was prepared by the synthetic method of intermediates G7, G11, the specific structure is shown in Table 4.

TABLE 4

Example 2: synthesis of Compound 1:

adding 0.01mol of raw material D1, 0.024mol of intermediate G1 and 1 × 10 mol into a 250ml three-mouth bottle under the protection of nitrogen^-4molPd(PPh₃)₄Stirring and mixing 100mL of toluene and 50mL of ethanol, dissolving 0.03mol of sodium carbonate in 50mL of water, then adding a sodium carbonate aqueous solution into a reaction system, heating to 110 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that no raw material D1 is left and the reaction is complete; naturally cooling to room temperature, filtering, layering the filtrate, taking an organic phase, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and purifying by a neutral silica gel column to obtain a target product, wherein the HPLC purity is 98.8%, and the yield is 57.7%;

elemental analysis Structure (molecular formula C)₄₆H₃₀N₂O): theoretical value C, 88.15; h, 4.82; n, 4.47; o, 2.55; test values are: c, 88.17; h, 4.81; n, 4.45; o, 2.57. ESI-MS (m/z) ((m/z))M⁺): theoretical value is 626.24, found 626.35.

Example 3: synthesis of Compound 4:

compound 4 was prepared as in example 2, except intermediate G2 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₂H₃₄N₂O): theoretical value C, 88.86; h, 4.88; n, 3.99; o, 2.28; test values are: c, 88.89; h, 4.87; n, 3.97; o, 2.27. ESI-MS (M/z) (M)⁺): theoretical value is 702.27, found 702.46.

Example 4: synthesis of compound 28:

compound 28 was prepared as in example 2, except intermediate G3 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.32; h, 4.64; n, 3.75; and O, 4.29. ESI-MS (M/z) (M)⁺): theoretical value is 742.26, found 742.33.

Example 5: synthesis of compound 30:

compound 30 was prepared as in example 2, except intermediate G4 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.33; h, 4.62; n, 3.76; and O, 4.29. ESI-MS (M/z) (M)⁺): theory of the inventionThe value was 742.26, found 742.41.

Example 6: synthesis of compound 49:

compound 49 was prepared as in example 2, except intermediate G5 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₁H₃₆N₂O): theoretical value C, 88.41; h, 5.24; n, 4.04; o, 2.31; test values are: c, 88.39; h, 5.25; n, 4.03; o, 2.33. ESI-MS (M/z) (M)⁺): theoretical value is 692.28, found 692.37.

Example 7: synthesis of compound 52:

compound 52 was prepared as in example 2, except intermediate G6 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.05; h, 5.22; n, 3.65; and O, 2.08. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.44.

Example 8: synthesis of compound 55:

compound 55 was prepared as in example 2, except intermediate G7 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.05; h, 5.21; n, 3.65; and O, 2.09. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.44.

Example 9: synthesis of compound 65:

compound 65 was prepared as in example 2, except intermediate G8 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.02; h, 5.24; n, 3.65; and O, 2.09. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.43.

Example 10: synthesis of compound 364:

compound 364 was prepared as in example 2, except intermediate G9 was used instead of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₃H₃₃N₃O₂): theoretical value C, 85.58; h, 4.47; n, 5.65; o, 4.30; test values are: c, 85.59; h, 4.48; n, 5.63; and O, 4.30. ESI-MS (M/z) (M)⁺): theoretical value is 743.26, found 743.35.

Example 11: synthesis of compound 700:

compound 700 was prepared as in example 2, except intermediate G10 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₃H₃₃N₃O₂): theoretical value C, 85.58; h, 4.47; n, 5.65; o, 4.30; test values are: c, 85.56; h, 4.48; n, 5.67; and O, 4.29. ESI-MS (M/z) (M)⁺): theoretical value is 743.26, found 743.33.

Example 12: synthesis of compound 1542:

compound 1542 is prepared as in example 2 except intermediate G11 is substituted for intermediate G1.

Elemental analysis Structure (molecular formula C)₅₂H₃₂N₄O₂): theoretical value C, 83.85; h, 4.33; n, 7.52; o, 4.30; test values are: c, 83.87; h, 5.31; n, 7.51; and O, 4.29. ESI-MS (M/z) (M)⁺): theoretical value is 744.25, found 744.40.

Example 13: synthesis of compound 1878:

compound 1878 is prepared as in example 2, except that starting material D2 is substituted for starting material D1 and intermediate G4 is substituted for intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.32; h, 4.62; n, 3.76; and O, 4.30. ESI-MS (M/z) (M)⁺): theoretical value is 742.26, found 742.32.

Example 14: synthesis of compound 7422:

compound 7422 is prepared as in example 2, except that starting material D3 is substituted for starting material D1 and intermediate G4 is substituted for intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.01; h, 5.25; n, 3.65; and O, 2.09. ESI-MS (M/z) (M)⁺): theoretical value of768.31, found 768.43.

Example 15: synthesis of compound 30':

compound 30' was prepared as in example 2, except intermediate G14 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.32; h, 4.63; n, 3.75; and O, 4.30. ESI-MS (M/z) (M)⁺): theoretical value is 742.26, found 742.42.

Example 16: synthesis of compound 52':

compound 52' was prepared as in example 2, except intermediate G15 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.01; h, 5.23; n, 3.66; o, 2.10. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.44.

Example 17: synthesis of compound 366':

compound 366' was prepared as in example 2, except intermediate G16 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₃H₃₃N₃O₂): theoretical value C, 85.58; h, 4.47; n, 5.65; o, 4.30; test values are: c, 85.59; h, 4.46; n, 5.64; o, 4.31. ESI-MS (M/z) (M)⁺): theory of the inventionThe value was 743.26, found 743.41.

Example 18: synthesis of compound 7422':

compound 7422' is prepared as in example 2, except that starting material D3 is substituted for starting material D1 and intermediate G14 is substituted for intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.01; h, 5.25; n, 3.65; and O, 2.09. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.37.

Example 19: synthesis of compound 28 ″:

compound 28 "was prepared as in example 2, except intermediate G18 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.33; h, 4.62; n, 3.75; and O, 4.30. ESI-MS (M/z) (M)⁺): theoretical value is 742.26, found 742.41.

Example 20: synthesis of compound 30 ″:

compound 30 "was prepared as in example 2, except intermediate G19 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₄H₃₄N₂O₂): theoretical value C, 87.31; h, 4.61; n, 3.77; o, 4.31; test values are: c, 87.33; h, 4.62; n, 3.75; and O, 4.30.ESI-MS(m/z)(M⁺): theoretical value is 742.26, found 768.44.

Example 21: synthesis of compound 52 ″:

compound 52 "was prepared as in example 2, except intermediate G20 was used in place of intermediate G1.

Elemental analysis Structure (molecular formula C)₅₇H₄₀N₂O): theoretical value C, 89.03; h, 5.24; n, 3.64; o, 2.08; test values are: c, 89.02; h, 5.23; n, 3.67; and O, 2.08. ESI-MS (M/z) (M)⁺): theoretical value is 768.31, found 768.41.

Example 22: synthesis of compound 2214 ":

compound 2214 "was prepared as in example 2, except that the starting material D1 was replaced with the starting material D2 and the intermediate G1 was replaced with the intermediate G21.

Elemental analysis Structure (molecular formula C)₅₃H₃₃N₃O₂): theoretical value C, 85.58; h, 4.47; n, 5.65; o, 4.30; test values are: c, 85.56; h, 4.48; n, 5.63; o, 4.33. ESI-MS (M/z) (M)⁺): theoretical value is 743.26, found 743.45.

Example 23: synthesis of compound 9606 ":

compound 9606 "was prepared as in example 2, except that the starting material D4 was used instead of the starting material D1 and the intermediate G21 was used instead of the intermediate G1.

Elemental analysis Structure (molecular formula C)₅₆H₃₉N₃O): theoretical value C, 87.36; h, 5.11; n, 5.46; the content of the oxygen is O,2.08 of; test values are: c, 87.32; h, 5.13; n, 5.45; o, 2.10. ESI-MS (M/z) (M)⁺): theoretical value is 769.31, found 769.41.

The organic compound is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as a hole transport layer material or an electron blocking material. The compound prepared in the example of the present invention and the existing material were respectively subjected to thermal performance, T1 level and HOMO level tests, and the results are shown in table 5.

TABLE 5

Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10^-5A toluene solution of (4); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level was tested by a photoelectron emission spectrometer (AC-2 type PESA) in an atmospheric environment.

As can be seen from the data in the table above, compared with the HT-1 and EB-1 materials applied at present, the organic compound prepared by the invention has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the material of the invention has a similar HOMO energy level as the existing application material, and also has a high triplet state energy level (T1), so that the energy loss of a light-emitting layer can be blocked, and the light-emitting efficiency of the device can be improved. Therefore, the triarylamine-containing organic material can effectively improve the luminous efficiency and prolong the service life of the OLED device after being applied to different functional layers of the OLED device.

The application effect of the synthesized OLED material in the device is explained in detail through device examples 1-22 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 22 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, keep the film thickness of the electrode material consistent, and are different in that the device embodiments 1 to 12 change the hole transport layer material in the device; device examples 13-22 were prepared by changing the electron blocking layer material of the devices, and the performance test results of the devices obtained in each example are shown in table 6.

Device example 1:

as shown in fig. 1, an electroluminescent device is prepared by the steps of:

a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;

b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3;

c) evaporating a hole transport material, namely the compound 1 of the invention, on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material is 80nm, and the layer is a hole transport layer 4;

d) evaporating an electron blocking material EB-1 on the hole transmission layer 4 in a vacuum evaporation mode, wherein the thickness of the electron blocking material EB-1 is 20nm, and the electron blocking layer 5 is formed on the hole transmission layer;

e) a luminescent layer 6 is evaporated on the electron blocking layer 5, the main materials are GH-1 and GH-2, the doping materials are GD-1, the mass ratio of GH-1, GH-2 and GD-1 is 45:45:10, and the thickness is 30 nm;

f) evaporating electron transport materials ET-1 and Liq on the light emitting layer 6 in a vacuum evaporation mode, wherein the mass ratio of ET-1 to Liq is 1:1, the thickness is 40nm, and the organic material of the layer is used as a hole blocking/electron transport layer 7;

g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8;

h) vacuum evaporating cathode Al (80nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9;

after completing the fabrication of the electroluminescent device according to the above procedure, the current efficiency and LT97 lifetime of the device were measured, and the results are shown in table 6. The molecular structural formula of the related material is shown as follows:

device example 2: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 28 prepared in example 4 as a hole transport material.

Device example 3: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 49 prepared in example 6 as a hole transport material.

Device example 4: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 52 prepared in example 7 as a hole transport material.

Device example 5: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 65 prepared in example 9 as a hole transport material.

Device example 6: the procedure of example 1 above was repeated except that the hole transporting layer 4 used the compound 1542 prepared in example 12 as a hole transporting material.

Device example 7: the procedure of example 1 above was repeated except that the hole transporting layer 4 used the compound 7422 prepared in example 14 as a hole transporting material.

Device example 8: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 52' prepared in example 16 as a hole transport material.

Device example 9: the procedure of example 1 above was repeated except that the hole transporting layer 4 used the compound 7422' prepared in example 18 as a hole transporting material.

Device example 10: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 28 "prepared in example 19 as a hole transport material.

Device example 11: the procedure of example 1 above was repeated except that the hole transport layer 4 used the compound 52 ″ prepared in example 21 as a hole transport material.

Device example 12: the procedure of example 1 above was repeated except that the hole transporting layer 4 used the compound 9606 "prepared in example 23 as a hole transporting material.

Device example 13: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 4 prepared in example 3 was used as an electron blocking material.

Device example 14: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 30 prepared in example 5 was used as an electron blocking material.

Device example 15: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 55 prepared in example 8 was used as an electron blocking material.

Device example 16: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; the electron blocking layer 5 used the compound 364 prepared in example 10 as an electron blocking material.

Device example 17: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 700 prepared in example 11 was used as an electron blocking material.

Device example 18: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; the electron-blocking layer 5 used the compound 1878 prepared in example 13 as an electron-blocking material.

Device example 19: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 30' prepared in example 15 was used as an electron blocking material.

Device example 20: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; the electron blocking layer 5 used the compound 366' prepared in example 17 as an electron blocking material.

Device example 21: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 30 "prepared in example 20 was used as an electron blocking material.

Device example 22: the procedure of example 1 above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material; electron blocking layer 5 the compound 2214 ″ prepared in example 22 was used as an electron blocking material.

Device comparative example 1: the procedure of example 1 described above was repeated except that the hole transport layer 4 used HT-1 as a hole transport material. The inspection data of the obtained electroluminescent device are shown in Table 6.

TABLE 6

Numbering	Current efficiency (cd/A)	Color(s)	LT97 Life (Hr) @5000nits
				Device example 1	65.3	Green light	110.2
Device example 2	67.3	Green light	123.7
				Device example 3	68.2	Green light	119.3
Device example 4	65.1	Green light	117.2
				Device example 5	68.6	Green light	110.8
Device example 6	65.3	Green light	126.3
				Device example 7	64.6	Green light	112.4
Device example 8	65.5	Green light	115.9
				Device example 9	68.3	Green light	120.7
Device example 10	62.2	Green light	116.2
				Device example 11	63.7	Green light	119.1
Device example 12	66.3	Green light	115.3
				Device example 13	70.8	Green light	120.7
Device example 14	72.7	Green light	118.7
				Device example 15	75.6	Green light	117.7
Device example 16	77.6	Green light	116.3
				Device example 17	72.1	Green light	115.2
Device example 18	72.9	Green light	111.5
				Device example 19	79.7	Green light	120.8
Device example 20	75.9	Green light	118.3
				Device example 21	71.7	Green light	111.7
Device example 22	70.9	Green light	119.6
				Device comparative example 1	58	Green light	80.5

From the results in table 6, it can be seen that the organic compound prepared by the present invention can be applied to the fabrication of OLED light emitting devices, and compared with comparative device example 1, the efficiency and lifetime of the organic compound are greatly improved compared with those of known OLED materials, especially the lifetime of the organic compound is greatly prolonged. Further, the OLED devices prepared by the material of the present invention can maintain long life at high temperature, and the results of high temperature driving life tests carried out on the device examples 1-22 and the device comparative example 1 at 85 ℃ are shown in Table 7.

TABLE 7

As can be seen from the data in table 7, device examples 1 to 22 are device structures in which the material of the present invention and a known material are combined, and compared with device comparative example 1, the OLED device provided by the present invention has a very good driving life at a high temperature.

Further experimental study shows that the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, and the results of efficiency tests of device examples 5, 10 and 17 and device comparative example 1 at the temperature range of-10 to 80 ℃ are shown in Table 8 and FIG. 2.

TABLE 8

As can be seen from the data in table 8, device examples 5, 10, and 17 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 not only high at low temperature, but also steadily increases during the temperature increase process.

In order to further test the beneficial effects of the compound of the present invention, the devices fabricated in the device example 1 and the device comparative example 1 were tested for leakage current under reverse voltage, and the test data is shown in fig. 3, which is a graph showing that, as shown in fig. 3, the device example 1 using the compound of the present invention has a smaller leakage current and a more stable current curve than the device fabricated in the device comparative example 1, so that the material of the present invention has a longer service life after being applied to the device fabrication. 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

1. A triarylamine compound is characterized in that the specific structure of the compound is as follows:

any one of the above.

2. An organic electroluminescent element comprising at least one functional layer containing a triarylamine compound according to claim 1.

3. The organic electroluminescent device as claimed in claim 2, wherein the triarylamine compound is used as a hole transport layer or an electron blocking layer material for manufacturing the organic electroluminescent device.

4. A lighting or display element, characterized in that the element comprises an organic electroluminescent device according to any one of claims 2 or 3.