CN111747936B - Substituted 1,3, 5-triazine compound, composition and application thereof - Google Patents

Substituted 1,3, 5-triazine compound, composition and application thereof Download PDF

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CN111747936B
CN111747936B CN201910251801.8A CN201910251801A CN111747936B CN 111747936 B CN111747936 B CN 111747936B CN 201910251801 A CN201910251801 A CN 201910251801A CN 111747936 B CN111747936 B CN 111747936B
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王悦
李成龙
张佐伦
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Jilin Yuanhe Electronic Material Co ltd
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Abstract

The invention discloses a substituted 1,3, 5-triazine compound, a composition and application thereof. The invention provides a 1,3, 5-triazine compound shown as a formula I. The 1,3, 5-triazine compound can be used as an electron transmission material and an electron acceptor material; the composite of the electron transport layer and the electron donor material can be prepared to be used as a main material of the electroluminescent device, and the electroluminescent device prepared by the method has the advantages of high efficiency, long service life and the like; furthermore, the 1,3, 5-triazine compound is used as an electron transport layer and is simultaneously used as a composition of an electron acceptor material and an electron donor material to construct a light-emitting layer, and the prepared electroluminescent device has the advantages of better high efficiency, longer service life and the like.

Description

Substituted 1,3, 5-triazine compound, composition and application thereof
Technical Field
The invention relates to a substituted 1,3, 5-triazine compound, a composition and application thereof.
Background
In the early sixties of the twentieth century, Pope et al first reported the phenomenon of organic electroluminescence, and they observed blue light emission from anthracene when a high voltage of four hundred volts was applied across a single crystal of anthracene (see m.pope, h.kallmann and p.magnane, j.chem.phys.,1963,38, 2042). However, since single crystals are difficult to grow and the driving voltage of devices is high, the processes used by them have little practical use. Until 1987, c.w.tang et al, Kodak corporation, usa, used an ultra-thin film technology to prepare a light emitting device using aromatic amine having a good hole transport effect as a hole transport layer, an aluminum complex of 8-hydroxyquinoline as a light emitting layer, and an Indium Tin Oxide (ITO) film and a metal alloy as an anode and a cathode, respectively. The device can obtain brightness up to 1000cd/m under 10V driving voltage2The efficiency of the device is 1.5lm/W (see C.W.Ta)ng and s.a.vanslyke, appl.phys.lett., 1987, 51, 913). This breakthrough development has led to the rapid and intensive worldwide development of organic electroluminescence research.
Research by Forrest et al at the university of princeton, 1998, has found that organic light-emitting devices prepared using common organic materials or using fluorescent dye doping techniques have a maximum light-emitting internal quantum efficiency of 25% due to the constraint of the quantum mechanical transition law of spin conservation. They doped the phosphorescent dye octaethylporphyrin platinum (PtOEP) into the host luminescent material to prepare a luminescent device with an external quantum efficiency of 4% and an internal quantum efficiency of 23%, thus opening up a new field of phosphorescent electroluminescence (see m.a. baldo, d.f. o' brienetal, Nature, 1998, 395, 151). However, on one hand, the phosphorescent material generally uses noble metals such as iridium and platinum, and is expensive, and on the other hand, the deep blue phosphorescent material still has the problems of chemical instability, large efficiency roll-off of the device under high current density, and the like, so that the development of an OLED device which uses cheap and stable organic small molecular materials and can realize high-efficiency light emission is very important.
The application of new materials in organic electroluminescent devices is a necessary means for promoting the continuous progress of electroluminescent technology and entering the practical stage. In recent years, great financial and energy has been put into the development of new materials, and a large number of materials with excellent properties have made some breakthrough progress in organic electroluminescence (see U.S. Pat. No.5,150,006; 5,141,671; 5,073,446; 5,061,569; 5,059,862; 5,059,861; 5,047,687; 4,950,950; 5,104,740; 5,227,252; 5,256,945; 5,069,975; 5,122,711; 5,554,450; 5,683,823; 5,593,788; 5,645,948; 5,451,343; 5,623,080; 5,395,862).
In recent years, with the wide application prospect in the fields of full-color display and solid-state white light illumination, the organic electroluminescent technology has been widely researched and paid attention to in the scientific research field and the industrial field. Organic small molecule photoelectric materials are widely used as high-performance materials due to the advantages of definite structure, easy modification, simple purification and processing and the like. At present, the conventional fluorescent dye molecules often have high fluorescence quantum yield, but the doped OLED devices are limited by 25% of internal quantum efficiency, and the external quantum efficiency is generally lower than 5%, which is far from the efficiency of the phosphorescent devices. Such as the red dye DCM (see c.w.tang, s.a.vanslyke, and c.h.chen, j.appl.phys.,1989,65, 3610; u.s.pat.no.5,908,581), device efficiency <10 cd/a; green dye quinacridone (see U.S. Pat. No.5,227,252; 5,593,788; CN 1482127A; CN 1219778; CN1660844), device efficiency <20cd/A, etc.
At present, a delayed fluorescence mechanism is mainly adopted in a fluorescent OLED device capable of breaking through the limitation of 25% of internal quantum efficiency, and the triplet excited state energy in the device can be effectively utilized. There are two main types of mechanisms, one is the TTA (Triplet-Triplet Annihilation) mechanism (see d.kondakoov, t.d.pawlik, t.k.hatwar, and j.p.spindler, j.appl.phys.,2009,106,124510). Another is the TADF (Thermally Activated Delayed Fluorescence) mechanism (see h.uoyama, k.goushi, k.shizu, h.nomura, c.adachi, nature, 2012,492,234). The TTA mechanism is a mechanism for improving the generation ratio of singlet excitons by utilizing the fusion of two triplet excitons, but the maximum internal quantum efficiency of the device is only 40-62.5%. The TADF mechanism is a mechanism that uses an organic small molecule material having a small singlet-triplet energy level difference (Δ EST), whose triplet excitons can be converted into singlet excitons through a process of reverse intersystem crossing (RISC) under ambient thermal energy. Theoretically, the quantum efficiency in the device can reach 100%. Generally, TADF molecules are doped mainly as guest materials in wide bandgap host materials to achieve high efficiency thermally activated delayed fluorescence (see q.zhang, j.li, k.shizu, s.huang, s.hirata, h.miyazaki, c.adachi, j.am.chem.soc.2012,134, 14706; h.uoyama, k.goushi, k.shizu, h.nomura, c.adachi, nature, 2012,492,234; t.nishimoto, t.yasuda, s.y.lee, r.kondo, c.adachi, mate.horiz, 2014,1, 264).
The performance of the electroluminescent device of the TADF material is remarkably improved compared with that of the traditional fluorescent device because the TADF material can emit light by simultaneously utilizing singlet excitons and triplet excitons. In addition, compared with the traditional phosphorescent material, the TADF material has low price, and is more beneficial to the popularization and application of commercialization. At present, TADF molecules with various light colors are synthesized from deep blue light to near infrared light, and partial device performances can be compared with those of the traditional phosphorescent device. Conventional single molecule TADF materials generally consist of two parts, a donor (D) and an acceptor (a) unit. Through careful molecular design, HOMO and LUMO orbitals are respectively concentrated at two ends of a donor and an acceptor to obtain smaller singlet triplet state energy level difference, so that effective reverse intersystem crossing is realized, and efficient TADF luminescence is realized. In addition, Exciplex (Exciplex) luminescence is a charge transfer excited state luminescence behavior between a donor molecule and an acceptor molecule, resulting from an electronic transition between the LUMO orbital of the acceptor molecule and the HOMO orbital of the donor molecule. Since the HOMO and LUMO orbitals of the exciplex are concentrated on the two donor and acceptor molecules, respectively, the corresponding singlet and triplet energy level differences tend to be smaller compared to single molecule TADF materials. Compared with a single-molecule TADF material, the exciplex can also realize high-efficiency heat-activated delayed fluorescence emission. The donor molecule and the acceptor molecule can not only form an exciplex to be used as a light emitting layer for emitting light, but also respectively serve as a hole transport layer and an electron transport layer, so that the structure of the device is simplified to a certain extent. In addition to luminescence through doping to form exciplexes, exciplex luminescence similar to that of a planar heterojunction (P-N) can also be generated at the molecular interface of the donor and acceptor (see: Advanced Materials,2016,28, 239-. Electroluminescent devices prepared with exciplex as the co-host have many advantages such as low turn-on, high efficiency, low roll-off, etc. and have become popular in the current research (see: Advanced Functional Materials,2015,25, 361-.
CN108218836A discloses two tris (phenyl/pyridine-benzimidazole) benzene/pyridine compounds (E1 and E2) as shown below, which can be used as electron acceptor and electron donor to form a light-emitting layer, and at the same time, can be used as electron transport for electroluminescent devices.
Figure BDA0002012591180000021
However, since the light-emitting layer is formed by compounding E1 or E2 as an electron acceptor and an electron donor, and E1 or E2 as an electron transport material, the efficiency of the prepared light-emitting device is low, and the stability of the device is poor.
The prior art (ACS Appl. Mater. interfaces 2018,10, 2151-.
Figure BDA0002012591180000031
The molecule as an electron acceptor material can be compounded with some electron donor materials to be used as a main material of an electroluminescent device, and meanwhile, the material can also be used as an electron transport layer for the electroluminescent device. However, the stability of the light-emitting device prepared by compounding the 3P-T2T molecule with some electron donor materials as the main material of the electroluminescent device and using the 3P-T2T molecule as the electron transport layer is poor.
CN106946859A discloses a series of triazine compounds substituted by bis-benzimidazole and its derivatives, and indicates that these compounds can be used as hole blocking layer and electron transport layer in electroluminescent devices, and these compounds can be used as light extraction layer or electron transport layer in electroluminescent devices, which can improve the efficiency of the devices to some extent. However, since single 4, 4' -dicarbazole biphenyl (CBP) is used as a host material, the electron transport capability of CBP is poor, and thus the device efficiency is still low.
CN102593374B discloses that three compounds (TPT-07, TBT-07 and TBT-14) shown in the specification are independently used as an electron transport layer and a host material for preparing an electroluminescent device. However, the efficiency of the resulting light emitting device is low.
Figure BDA0002012591180000032
Therefore, the device performance of the exciplex is still to be improved compared to the single-molecule TADF material.
Disclosure of Invention
The invention provides a 1,3, 5-triazine compound, a composition and application thereof, aiming at solving the defects of insufficient electron acceptor materials and electron transport materials in the prior art. The 1,3, 5-triazine compound not only can be used as an electron transport material for preparing an electron transport layer of an electroluminescent device, but also can be used as an electron acceptor material, and a composition of the electron acceptor material and an electron donor material can be used as a main material of the electroluminescent device, so that the prepared electroluminescent device has the advantages of high efficiency, long service life and the like; furthermore, the 1,3, 5-triazine compound is used as an electron transport layer and is simultaneously used as a composition of an electron acceptor material and an electron donor material to construct a light-emitting layer, and the prepared electroluminescent device has the advantages of better high efficiency, longer service life and the like.
The present invention solves the above-mentioned problems by the following technical means.
The invention provides a 1,3, 5-triazine compound shown in a formula I,
Figure BDA0002012591180000041
wherein L is a single bond or
Figure BDA0002012591180000042
Ring A is phenyl, substituted by one or more Rd-1Substituted phenyl, 6 membered monocyclic heteroaryl, or substituted with one or more Rd-2A substituted 6 membered monocyclic heteroaryl; said 6 membered monocyclic heteroaryl is substituted with one or more Rd-2The heteroatom in "6-membered monocyclic heteroaryl" in a substituted 6-membered monocyclic heteroaryl is defined as: the number of the heteroatoms is 1-3; when R isd-1And Rd-2Independently a plurality of the same or different;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22and R23Independently hydrogen, deuterium, halogen, cyano, C1～C10Alkyl, by one or more Ra-1Substituted C1～C10Alkyl radical, C1～C10alkyl-O-, with one or more Ra-2Substituted C1～C10alkyl-O-, C6～C14Aryl radicals, substituted by one or more Ra-3Substituted C6～C14Aryl, 5-6 membered monocyclic heteroaryl, substituted with one or more Ra-4Substituted 5-6 membered monocyclic heteroaryl or
Figure BDA0002012591180000043
Said 5-6 membered monocyclic heteroaryl is substituted with one or more Ra-4The heteroatom in "5-6 membered monocyclic heteroaryl" in a substituted 5-6 membered monocyclic heteroaryl is defined as: the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4; when R isa-1、Ra -2、Ra-3And Ra-4Independently a plurality thereof, the same or different; wherein the content of the first and second substances,
Figure BDA0002012591180000044
is composed of
Figure BDA0002012591180000045
And
Figure BDA0002012591180000046
connected by a single bond;
R24independently is
Figure BDA0002012591180000047
n1 and n2 are independently 1,2, 3 or 4; n3 is 1,2 or 3;
R1-1、R2-1、R1-2、R2-2、R1-3、R1-4、R2-3independently isHydrogen, deuterium, halogen, cyano, C1～C10Alkyl, by one or more Rb-1Substituted C1～C10Alkyl radical, C1～C10alkyl-O-, with one or more Rb-2Substituted C1～C10alkyl-O-, C6～C14Aryl radicals, substituted by one or more Rb-3Substituted C6～C14Aryl, 5-6 membered monocyclic heteroaryl, substituted with one or more Rb-4A substituted 5-6 membered monocyclic heteroaryl, or
Figure BDA0002012591180000051
Said 5-6 membered monocyclic heteroaryl is substituted with one or more Rb-4The heteroatom in "5-6 membered monocyclic heteroaryl" in a substituted 5-6 membered monocyclic heteroaryl is defined as: the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4; when R isb-1、Rb-2、Rb-3And Rb-4When there are plural, Rb-1、Rb-2、Rb-3And Rb-4Independently are the same or different; wherein the content of the first and second substances,
Figure BDA0002012591180000052
is composed of
Figure BDA0002012591180000053
And
Figure BDA0002012591180000054
connected by a single bond;
Figure BDA0002012591180000055
independently of the others, phenyl, substituted by one or more Rc-1Substituted phenyl, 5-6 membered monocyclic heteroaryl, or substituted with one or more Rc-2A substituted 5-6 membered monocyclic heteroaryl; said 5-6 membered monocyclic heteroaryl is substituted with one or more Rc-2The heteroatom in "5-6 membered monocyclic heteroaryl" in a substituted 5-6 membered monocyclic heteroaryl is defined as: the number of the heteroatoms is 1-3; when R isc-1And Rc-2Independently a plurality thereof, the same or different;
Ra-1、Ra-2、Ra-3、Ra-4、Rb-1、Rb-2、Rb-3、Rb-4、Rc-1、Rc-2、Rd-1and Rd-2Independently the following substituents: deuterium, halogen, cyano, trifluoromethyl, C1～C6Alkyl or C1～C6alkyl-O-.
In the invention, the definitions of some substituents in the 1,3, 5-triazine compounds shown in the formula I can be described as follows, and the definitions of the substituents which are not mentioned are described in any scheme above.
In one embodiment of the invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently halogen, said halogen (e.g. fluorine, chlorine, bromine or iodine) is independently fluorine.
In one embodiment of the invention, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently halogen, said halogen (e.g. fluorine, chlorine, bromine or iodine) is independently fluorine.
In one embodiment of the invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently is C1～C10Alkyl, by one or more Ra-1Substituted C1～C10Alkyl radical, C1～C10alkyl-O-or by one or more Ra-2Substituted C1～C10In alkyl-O-, said C1～C10Alkyl is independently C1～C6Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl or hexyl), preferably C1～C4The alkyl group of (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl) is more preferably methyl or isopropyl.
In one embodiment of the invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently is C6～C14Aryl radicals or by one or more Ra-3Substituted C6～C14In aryl, said C6～C14Aryl is independently C6～C10An aryl group; such as phenyl or naphthyl.
In one embodiment of the invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently is a 5-6 membered monocyclic heteroaryl or substituted with one or more Ra-4In the substituted 5-6 membered monocyclic heteroaryl, said C1～C12The heteroaryl is independently heteroatom selected from N, and the number of heteroatoms is 1-3; preferably a pyridyl group.
In one embodiment of the invention, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently is C1～C10Alkyl, by one or more Rb-1Substituted C1～C10Alkyl radical, C1～C10alkyl-O-or by one or more Rb-2Substituted C1～C10In alkyl-O-, said C1～C10Alkyl is independently C1～C6Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl or hexyl), preferably C1-C4The alkyl group of (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl) is more preferably methyl or isopropyl.
In one embodiment of the invention, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently is C6～C14Aryl radicals or by one or more Rb-3Substituted C6～C14In aryl, said C6～C14Aryl is independently C6～C10An aryl group; such as phenyl or naphthyl.
In one embodiment of the invention, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently is a 5-6 membered monocyclic heteroaryl or substituted with one or more Rb-4In the substituted 5-6 membered monocyclic heteroaryl, said C1～C12The heteroaryl is independently heteroatom selected from N, and the number of heteroatoms is 1-3; preferably a pyridyl group.
In one embodiment of the invention, ring A is 6-membered monocyclic heteroaryl or substituted with one or more Rd-2In the substituted 6-membered monocyclic heteroaryl, the 6-membered monocyclic heteroaryl is independently a heteroatom selected from N, and the number of heteroatoms is 1-2; preferably a pyridyl group.
In one embodiment of the present invention, when
Figure BDA0002012591180000061
When the aryl is a phenyl group independently, the phenyl group,
Figure BDA0002012591180000062
independently is
Figure BDA0002012591180000063
(e.g. in
Figure BDA0002012591180000064
Figure BDA0002012591180000065
In one embodiment of the present invention,
Figure BDA0002012591180000066
independently is a 5-6 membered monocyclic heteroaryl or substituted with one or more Rc-2In the substituted 5-6 membered monocyclic heteroaryl, the 5-6 membered monocyclic heteroaryl is independently heteroatom selected from N, and the number of heteroatoms is 1-2; preferably a pyridyl group.
In one embodiment of the present invention,
Figure BDA0002012591180000067
R21、R22and R23The same is true.
In one embodiment of the invention, when L is
Figure BDA0002012591180000068
When R is24Independently located at
Figure BDA0002012591180000069
And
Figure BDA00020125911800000610
ortho, meta or para to the attachment site.
In one embodiment of the invention, Ra-1、Ra-2、Ra-3、Ra-4、Rb-1、Rb-2、Rb-3、Rb-4、Rc-1、Rc-2、Rd-1And Rd-2Independently halogen, said halogen (e.g. fluorine, chlorine, bromine or iodine) is independently fluorine.
In one embodiment of the invention, Ra-1、Ra-2、Ra-3、Ra-4、Rb-1、Rb-2、Rb-3、Rb-4、Rc-1、Rc-2、Rd-1And Rd-2Independently is C1～C6Alkyl or C1～C6In alkyl-O-, said C1～C6Alkyl or C1～C6C in alkyl-O-)1～C6Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, or hexyl) is independently C1～C4The alkyl group of (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl) is more preferably methyl or isopropyl.
In one embodiment of the invention, Ra-1、Ra-2、Ra-3、Ra-4、Rb-1、Rb-2、Rb-3、Rb-4、Rc-1、Rc-2、Rd-1And Rd-2Independently of the number of (a) is 1,2 or 3.
In one embodiment of the invention, when R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently by one or more Ra-1Substituted C1～C10Alkyl or by one or more Ra-2Substituted C1～C10alkyl-O-, said substituted C1～C10Alkyl or substituted C1～C10Substituted C in alkyl-O-)1～C10Alkyl is independently trifluoromethyl.
In one embodiment of the invention, when R is1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Standing by one or more Rb-1Substituted C1～C10Alkyl or by one or more Rb-2Substituted C1～C10alkyl-O-, said substituted C1～C10Alkyl or substituted C1～C10Substituted C in alkyl-O-)1～C10Alkyl is independently trifluoromethyl.
In one embodiment of the invention, R1-1、R1-2、R1-3And R1-4Independently of one another is hydrogen, deuterium, C1～C10Alkyl, by one or more Rb-1Substituted C1～C10Alkyl radical, C6～C14Aryl radicals, substituted by one or more Rb-3Substituted C6～C14Aryl, 5-6 membered monocyclic heteroaryl, substituted with one or more Rb-4Substituted 5-6 membered monocyclic heteroaryl or
Figure BDA0002012591180000071
R2-1、R2-2And R2-3Independently hydrogen.
In one embodiment of the present invention,
Figure BDA0002012591180000072
independently is
Figure BDA0002012591180000073
Figure BDA0002012591180000074
Figure BDA0002012591180000075
Preferably is
Figure BDA0002012591180000076
Figure BDA0002012591180000077
Figure BDA0002012591180000081
In one embodiment of the present invention,
Figure BDA0002012591180000082
independently is
Figure BDA0002012591180000083
Figure BDA0002012591180000084
Figure BDA0002012591180000085
Preferably is
Figure BDA0002012591180000086
Figure BDA0002012591180000087
Figure BDA0002012591180000091
In one embodiment of the present invention,
Figure BDA0002012591180000092
independently is
Figure BDA0002012591180000093
In one embodiment of the invention, ring A is phenyl or substituted with one or more Rd-1A substituted phenyl group.
In one embodiment of the invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently hydrogen, deuterium, halogen, cyano, C1～C10Alkyl, by one or more Ra-1Substituted C1～C10Alkyl radical, C6～C14Aryl radicals or by one or more Ra-3Substituted C6～C14An aryl group; preferably hydrogen or halogen.
In one embodiment of the invention, R24Independently is
Figure BDA0002012591180000094
In one embodiment of the invention, L is a single bond or
Figure BDA0002012591180000095
Ring A is phenyl or substituted by one or more Rd-1Substituted phenyl;
Figure BDA0002012591180000096
same as R21、R22And R23The same;
R24independently is
Figure BDA0002012591180000097
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently hydrogen, deuterium, halogen, cyano, C1～C10Alkyl, quiltOne or more Ra-1Substituted C1～C10Alkyl radical, C6～C14Aryl radicals or by one or more Ra-3Substituted C6～C14An aryl group; preferably hydrogen, deuterium, halogen.
In one embodiment of the present invention, the 1,3, 5-triazine compound represented by formula I is any one of the following compounds:
Figure BDA0002012591180000098
Figure BDA0002012591180000101
Figure BDA0002012591180000111
Figure BDA0002012591180000121
the compound of formula I of the invention can be prepared according to conventional chemical synthesis methods in the field, and the steps and conditions thereof can refer to the steps and conditions of similar reactions in the field.
The invention provides a preparation method of a 1,3, 5-triazine compound shown as a formula I, which can comprise any scheme as follows:
scheme one, the synthetic route is as follows:
Figure BDA0002012591180000131
scheme two, the synthetic route is as follows:
Figure BDA0002012591180000132
scheme three, the synthetic route is shown below:
Figure BDA0002012591180000141
scheme four, the synthetic route is shown below:
Figure BDA0002012591180000142
wherein R is1’And R2’Is as defined for R1、R2、R3、R4、R5、R6、R7、R8、R9And R10，R1-1、R2-1、R1-2、R2-2、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10N1, n2 and n3 are as defined above, and m1 and m2 are independently 0, 1,2, 3 or 4.
The invention provides application of a 1,3, 5-triazine compound shown as a formula I as an electronic material.
In one embodiment of the present invention, the electron material serves as an electron transport material and/or an electron acceptor material; preferably an electron transporting material and/or an electron acceptor material in an organic electroluminescent device.
The invention provides application of a 1,3, 5-triazine compound shown as a formula I in the field of organic electroluminescent devices.
In one embodiment of the invention, the 1,3, 5-triazine compound shown in the formula I is used for preparing one or more of an electron transport layer, a hole blocking layer and a light emitting layer in an organic electroluminescent device.
The invention provides an organic electroluminescent composition, which comprises an electron donor material and a 1,3, 5-triazine compound shown in a formula I.
In one embodiment of the present invention, the electron donor material in the organic electroluminescent composition may be a phenyl or naphthyl carbazole type electron donor material conventional in the art; the phenyl or naphthyl carbazole electron donor material preferably contains 2-3 phenyl carbazole or naphthyl carbazole structures; the phenyl or naphthyl carbazole electron donor material is preferably any one of the following compounds:
Figure BDA0002012591180000151
Figure BDA0002012591180000161
in the present invention, the molar ratio of the 1,3, 5-triazine compound represented by formula I to the electron donor material can be a molar ratio conventional in the art (for example, a molar ratio of the electron acceptor material to the electron donor material in an exciplex conventional in the art), and preferably, the molar ratio of the 1,3, 5-triazine compound represented by formula I to the electron donor material is 3:1 to 1: 3; preferably 1: 1.
In one embodiment of the present invention, the organic electroluminescent composition may further comprise a doped luminescent material; the doped luminescent material may be a doped luminescent material conventional in the art, such as a fluorescent luminescent material and/or a phosphorescent luminescent material (also referred to as a phosphorescent complex luminescent material).
In the present invention, the mass percentage of the doped luminescent material in the organic electroluminescent composition may be a mass percentage that is conventional in the art, and when the doped luminescent material is a fluorescent luminescent material, the mass percentage of the doped luminescent material in the composition is preferably 0.5WT％-2.0WT% (e.g. 1)WT%); when the doped luminescent material is a phosphorescent luminescent material, the mass percentage of the doped luminescent material in the composition is preferably 5.0WT％-15.0WT% (e.g. 10)WT％)。
In one embodiment of the present invention, in the doped luminescent material, the phosphorescent luminescent material may be a phosphorescent luminescent material conventional in the art, and in the present invention, any one of the following compounds is preferred:
Figure BDA0002012591180000162
Figure BDA0002012591180000171
wherein, Ra1、Ra3、Rb1、Rb3、Rd1、Rd3、Re4、Re5、Re6、Rf7、Rf8、Rf9、Rb10-1、Rb10-2、Re10-1、Re10-2、Rf10-1And Rf10-2Independently H or a linear or branched alkyl group containing 1-5C;
Ra2、Rb2and Rd2Independently H, straight or branched chain alkyl containing 1-5C, phenyl or phenyl substituted by straight or branched chain alkyl containing 1-5C;
Figure BDA0002012591180000172
independently a six-membered aromatic heterocyclic ring containing 1-2N.
In one embodiment of the present invention, in the doped luminescent material, the phosphorescent luminescent material is IrPPy3
Figure BDA0002012591180000173
In one embodiment of the present invention, in the doped luminescent material, the fluorescent luminescent material may be a fluorescent luminescent material conventional in the art, and in the present invention, any one of the following compounds is preferred:
Figure BDA0002012591180000174
Figure BDA0002012591180000181
wherein Rg11-1、Rg11-2、Rh11-1、Rh11-2Independently a straight or branched chain alkyl group containing 1 to 5 carbons;
Rg12-1、Rg12-2、Rh13-1、Rh13-2、Rh13-3and Rh13-4Represents a linear or branched alkyl group containing 1 to 5C, F or CF3；
Ri14-1、Ri14-2、Ri15-1、Ri15-2、Rj16-1、Rj16-2、Rj17-1、Rj17-2、Rk18-1、Rk18-2、Rk18-3、Rk18-4、Rk19-1、Rk19-2、Rk19-3、Rk19-4、Rl20-1、Rl20-2、Rl20-3、Rl20-4、Rm23-1、Rm24-1、Rn26-1、Rn27-1、Ro29-1、Ro30-1、Ro32-1、Rp34-1、Rp35-1、Rp36-1And Rp37-1Independently a linear or branched alkyl group containing 1 to 5C, cyclohexane or cumene;
Rm22-1、Rn25-1、Ro28-11and Rp33-1Is a straight chain or branched chain alkyl containing 1-4C.
In one embodiment of the present invention, in the doped luminescent material, the fluorescent luminescent material is
Figure BDA0002012591180000182
The invention provides an application of the organic electroluminescent composition as an organic electroluminescent material.
In one embodiment of the present invention, the organic electroluminescent material is used for preparing a light-emitting layer in an organic electroluminescent device.
The invention provides an organic electroluminescent device which contains the organic electroluminescent composition.
In one embodiment of the present invention, the organic electroluminescent composition is a light-emitting layer (the light-emitting layer is based on an intermolecular charge transfer excited state formed by an Exciplex, which is an Exciplex formed by an electron donor molecule and an electron acceptor molecule).
In one embodiment of the present invention, the organic electroluminescent device further includes a substrate, and an anode layer, an organic light emitting functional layer, and a cathode layer sequentially formed on the substrate; the organic light-emitting functional layer comprises the light-emitting layer, and can also comprise any one or a combination of more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer; preferably, the electron transport material in the electron transport layer has the same structure as the 1,3, 5-triazine compound in the organic electroluminescent composition.
The invention provides an application of the organic electroluminescent device in an organic electroluminescent display or an organic electroluminescent lighting source.
It will be understood by those skilled in the art that, in accordance with the convention used in the art, the structural formulae used in the radicals described herein
Figure BDA0002012591180000191
Means that the corresponding group is linked to other fragments, groups in compound I via this site.
In the present invention, the number of said "substitution" may be one or more unless otherwise specified; when there are plural, there may be 2, 3 or 4.
In the present invention, when the number of the "substitution" is plural, the "substitution" may be the same or different.
In the present invention, the position of "substitution" may be arbitrary unless otherwise specified.
In the present invention, unless otherwise specified, the hydrogen or H is hydrogen in natural abundance, i.e., a mixture of isotopes protium, deuterium and tritium, wherein the abundance of protium is 99.98%.
In the invention, the deuterium is D or2H, also known as deuterium.
In the present invention, the abundance of deuterium at deuterium substitution sites is greater than 99%.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Radical definition
Definitions for the terms of the standardization sector can be found in the literature references including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4TH ED." Vols.A (2000) and B (2001), Plenum Press, New York.
In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the formula is written from right to left.
The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including but not limited to patents, patent applications, articles, books, operating manuals, and treatises, are hereby incorporated by reference in their entirety.
Certain chemical groups defined herein are preceded by a shorthand notation to indicate the total number of carbon atoms present in the group. E.g. C1～C6Alkyl refers to an alkyl group as defined below having a total of 1,2, 3,4, 5, or 6 carbon atoms. The total number of carbon atoms in the shorthand notation excludes carbons that may be present in a substituent of the group.
Numerical ranges defined in the substituents herein, such as 0 to 4, 1-4, 1 to 3, etc., indicate integers within the range, such as 1-6 being 0, 1,2, 3,4, 5, 6.
In addition to the foregoing, the following terms, when used in the specification and claims of this application, have the meanings indicated below, unless otherwise specifically indicated.
In the present application, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
In this application, the term "alkyl" as a group or part of another group (e.g., as used in halo-substituted alkyl and the like groups) is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. E.g. C1～C10. As in "C1～C6Alkyl is defined to include groups having 1,2, 3,4, 5, or 6 carbon atoms in a straight or branched chain configuration. For example, in the present invention, said C1～C6Each alkyl is independently methyl, ethyl, propyl, butyl, pentyl or hexyl; wherein propyl is C3Alkyl (including isomers such as n-propyl or isopropyl); butyl being C4Alkyl (including isomers such as n-butyl, sec-butyl, isobutyl, or tert-butyl); pentyl is C5Alkyl (including isomers such as n-pentyl, 1-methyl-butyl, 1-ethyl-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, isopentyl, tert-pentyl or neopentyl); hexyl is C6Alkyl (including isomers such as n-hexyl or isohexyl).
In this application, the term "aryl" as a group or part of another group refers to a 4n +2 aromatic ring system (e.g., having 6, 10, or 14 shares in a cyclic array) having 6-14 ring atoms and zero heteroatoms provided in the aromatic ring system, either monocyclic or polycyclic (e.g., bicyclic or tricyclic)p electrons) ("C)6～C14Aryl "). Examples of the above aryl unit include phenyl, naphthyl, phenanthryl, or anthryl.
In this application, the term "heteroaryl" as a group or part of another group refers to a group of a 5-6 membered monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n +2 aromatic ring system ("5-6 membered heteroaryl") having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur. Heteroaryl groups within the scope of this definition include, but are not limited to: acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, indolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinoline.
The terms "moiety," "structural moiety," "chemical moiety," "group," "chemical group" as used herein refer to a specific fragment or functional group in a molecule. Chemical moieties are generally considered to be chemical entities that are embedded in or attached to a molecule.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is standard in the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
It should be understood that as used herein, singular forms, such as "a", "an", include plural references unless the context clearly dictates otherwise. Furthermore, the term "comprising" is open-ended, i.e. including what is specified in the invention, but not excluding other aspects.
The present invention employs conventional methods of mass spectrometry, elemental analysis, and the various steps and conditions can be referred to those conventional in the art unless otherwise indicated.
Unless otherwise indicated, the present invention employs standard nomenclature for analytical chemistry, organic synthetic chemistry, and optics, and standard laboratory procedures and techniques. In some cases, standard techniques are used for chemical synthesis, chemical analysis, light emitting device performance detection.
The compounds of the present invention may contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may be labelled with radioisotopes, such as deuterium (g) ((R))2H) In that respect All isotopic variations of the compounds of the present invention, whether radioactive or not, are intended to be encompassed within the scope of the present invention.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the substituted 1,3, 5-triazine compound shown in the formula I has good electron accepting capacity and electron transporting capacity; and has good thermal stability (the thermal decomposition temperature of all compounds is between 420 ℃ and 440 ℃). The compounds can be used in the field of organic electroluminescence. The organic electroluminescent material can be independently used as an electron transport layer or a hole blocking layer, or can be compounded with an electron donor material to form a composite host material which can be independently used for an organic electroluminescent device, and the composite host material can be doped with some luminescent materials (including phosphor and fluorescent materials) to form a luminescent layer of the organic electroluminescent material. Therefore, the material can be simultaneously used as a functional material to be applied to a luminescent layer and an electron transport layer/hole blocking layer of an electroluminescent device, and has the advantages that the electron transport layer and an electron acceptor material in the luminescent layer belong to the same molecule, so that a potential barrier is not needed when electrons enter the luminescent layer from the electron transport layer, and the driving voltage and the efficiency roll-off of the luminescent device are favorably reduced, and the efficiency and the service life of the device are improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Figure BDA0002012591180000211
10mL of water dissolved NaHSO3(4.70g, 45.0mmol), 0.175g (1.65mmol) of benzaldehyde was added, and the mixture was stirred at room temperature for 5 hours. Then adding N1- (3, 5-dibromophenyl) -1, 2-phenylenediamine 0.513g (1.50mmol), 40mL of ethanol are added, and the mixture is refluxed for 24 hours under the protection of nitrogen. After cooling to room temperature, filtration gave 0.578g (yield 90.0%) of a crude white product.
0.428g (1.00mmol) of the crude product, 1.02g (4.00mmol) of pinacol diboron, 1.96g (20.0mmol) of dried potassium acetate and 120mL of dried 1, 4-dioxane were placed in a 250mL two-necked flask, and 146mg (0.20mmol) of the catalyst [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (ll) was added under nitrogen protection, and the mixture was refluxed for 24 hours. After cooling to room temperature, potassium acetate was removed by filtration, dioxane was removed from the filtrate, and the filtrate was washed with dichloromethane/water, and the organic phase was removed of the organic solvent, and column chromatography was performed using dichloromethane as a developing solvent to obtain 437mg (yield 83.7%) of a white solid intermediate.
418mg (0.800mmol) of the above white intermediate, 0.534g (2.00mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and 331mg (2.40mmol) of potassium carbonate were put in a 100mL two-necked flask, and 25mL of THF and H were added2O2 mL, adding catalyst tetrakis (triphenylphosphine) palladium 30.0mg under nitrogen, and refluxing for 24 h. The reaction mixture was washed with dichloromethane/water, and the organic phase was subjected to solvent removal and column chromatography to obtain 425mg (yield 72.5%) of a white solid compound. The mass of the molecular ions determined by mass spectrometry was: 732.40 (calculated value: 732.27); theoretical element content (%) C49H32N8: c, 80.31; h, 4.40; n, 15.29; measured elemental content (%): c, 80.22; h, 4.35; n, 15.27. The above analysis results show that the obtained product is the target product.
Example 2
Figure BDA0002012591180000221
10mL of water dissolved NaHSO3(4.70g, 45.0mmol), 0.792g (3.00mmol) of 3, 5-dibromobenzaldehyde is added, and the mixture is stirred at normal temperature for 5 h. Then 0.607g (3.30mmol) of o-aminodiphenylamine is added, 40mL of ethanol is added, and the mixture is refluxed for 24 hours under the protection of nitrogen. After cooling to room temperature, filtration gave 1.13g (88.3% yield) of a crude white product.
0.856g (2.00mmol) of the crude product, 2.03g (8.00mmol) of pinacol diboron, 3.92g (40.0mmol) of dried potassium acetate, and 120mL of dried 1, 4-dioxane were placed in a 250mL two-necked flask, and 293mg (0.40mmol) of the catalyst [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (ll) was added under nitrogen protection, and the mixture was refluxed for 24 hours. After cooling to room temperature, potassium acetate was removed by filtration, dioxane was removed from the filtrate, and the filtrate was washed with dichloromethane/water, and the organic phase was removed of the organic solvent, and column chromatography was performed using dichloromethane as a developing agent to obtain 845mg (yield 81.2%) of a white solid intermediate.
783mg (1.50mmol) of the above white intermediate, 1.00g (3.75mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and 621mg (4.5mmol) of potassium carbonate were put in a 100mL two-necked flask, and THF 25mL, H were added2O3 mL, adding 50.0mg of catalyst tetrakis (triphenylphosphine) palladium under nitrogen, and refluxing for 12 h. The reaction mixture was washed with dichloromethane/water, and the organic phase was subjected to solvent removal and column chromatography to obtain 725mg (yield 66.0%) of a white solid. The mass of the molecular ions determined by mass spectrometry was: 732.58 (calculated value: 732.27); theoretical element content (%) C49H32N8: c, 80.31; h, 4.40; n, 15.29; measured elemental content (%): c, 80.50; h, 4.35; n, 15.33. The above analysis results show that the obtained product is the target product.
Example 3
Figure BDA0002012591180000222
Following the synthesis of example 2, following the same procedure, the compound N- (3-pyridyl) -1, 2-phenylenediamine was used instead of the compound o-aminodiphenylamine to afford 1.00g (66.7% yield) of the white compound having a molecular ion mass determined by mass spectrometry of: 733.28 (calculated value: 733.27); theory of the inventionElement content (%) C48H31N9: c, 78.56; h, 4.26; n,17.18, measured elemental content (%): c, 78.75; h, 4.41; n, 16.93. The above analysis results show that the obtained product is the target product.
Example 4
Figure BDA0002012591180000223
Following the synthesis of example 2, the procedure was the same, substituting the compound N- (4-pyridyl) -1, 2-phenylenediamine for the compound o-aminodiphenylamine to provide 0.628g (57.2% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 733.33 (calculated value: 733.27); theoretical element content (%) C48H31N9: c, 78.56; h, 4.26; n,17.18, measured elemental content (%): c, 78.58; h, 4.34; and N, 17.25. The above analysis results show that the obtained product is the target product.
Example 5
Figure BDA0002012591180000231
Following the synthesis of example 1, following the same procedure, compound 3-aldehyde pyridine was used instead of compound benzaldehyde to give 0.537g (48.9% yield) of a white compound with a mass of molecular ions determined by mass spectrometry: 733.15 (calculated value: 733.27); theoretical element content (%) C48H31N9: c, 78.56; h, 4.26; n,17.18, measured elemental content (%): c, 78.75; h, 4.41; n, 16.93. The above analysis results show that the obtained product is the target product.
Example 6
Figure BDA0002012591180000232
Synthesis according to example 1, the same procedure was followed, using the compound 4-formylpyridine instead of the compound benzaldehyde, to give 0.523g of a white compound (product yield)Rate 66.7%), mass spectrometry determined the molecular ion mass as: 733.19 (calculated value: 733.27); theoretical element content (%) C48H31N9: c, 78.56; h, 4.26; n,17.18, measured elemental content (%): c, 78.66; h, 4.40; and N, 16.97. The above analysis results show that the obtained product is the target product.
Example 7
Figure BDA0002012591180000233
The synthesis according to example 1, following the same procedure, was followed, substituting compound benzaldehyde with compound 2-fluorobenzaldehyde to give 1.033g (68.9% yield) as a white compound having a mass of molecular ions determined by mass spectrometry: 750.22 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c, 78.48; h, 4.06; f, 2.55; n, 14.94. The above analysis results show that the obtained product is the target product.
Example 8
Figure BDA0002012591180000241
The synthesis according to example 1, following the same procedure, substituting the compound benzaldehyde with the compound 3-fluorobenzaldehyde, gave 0.880g (58.7% yield) of the white compound, having a mass of molecular ions determined by mass spectrometry of: 750.09 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c,78.42H, 4.11; f, 2.55; n, 14.83. The above analysis results show that the obtained product is the target product.
Example 9
Figure BDA0002012591180000242
Synthesis according to example 1In the same manner, the compound 4-fluorobenzaldehyde was used instead of the compound benzaldehyde, to obtain 0.672g (yield 44.8%) of a white compound, and the mass of molecular ions determined by mass spectrometry was: 750.25 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c, 78.44; h, 4.25; f, 2.77; n, 14.88. The above analysis results show that the obtained product is the target product.
Example 10
Figure BDA0002012591180000243
The synthesis according to example 1, following the same procedure, using the compound 3, 5-difluorobenzaldehyde instead of the compound benzaldehyde, gave 0.597g (39.8% yield) of white compound with a mass spectrometric analysis determining the mass of the molecular ion: 768.33 (calculated value: 768.26); theoretical element content (%) C49H30F2N8: c, 76.55; h, 3.93; f, 4.94; n,14.57, measured elemental content (%): c, 76.53; h, 3.91; f, 4.58; n, 14.68. The above analysis results show that the obtained product is the target product.
Example 11
Figure BDA0002012591180000244
Following the synthesis of example 2, following the same procedure, the compound N- (2-fluorophenyl) -1, 2-phenylenediamine was used instead of the compound o-aminodiphenylamine to give 0.672g (44.8% yield) of the white compound having a molecular ion mass determined by mass spectrometry of: 750.34 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c, 78.25; h, 4.21; f, 2.39; n, 14.77. The above analysis results show that the obtained product is the target product.
Example 12
Figure BDA0002012591180000251
The synthesis according to example 2, following the same procedure, using the compound N- (3-fluorophenyl) -1, 2-phenylenediamine instead of the compound o-aminodiphenylamine, gave 0.754g (50.3% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 750.12 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c, 78.54; h, 4.20; f, 2.44; n, 14.97. The above analysis results show that the obtained product is the target product.
Example 13
Figure BDA0002012591180000252
Following the synthesis of example 2, following the same procedure, the compound N- (4-fluorophenyl) -1, 2-phenylenediamine was used instead of the compound o-aminodiphenylamine to give 0.724g (48.3% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 750.19 (calculated value: 750.27); theoretical element content (%) C49H31FN8: c, 78.38; h, 4.16; f, 2.53; n,14.92, measured elemental content (%): c, 78.52; h, 4.14; f, 2.57; n, 14.85. The above analysis results show that the obtained product is the target product.
Example 14
Figure BDA0002012591180000253
The synthesis according to example 2, following the same procedure, using the compound N- (3, 5-difluorophenyl) -1, 2-phenylenediamine instead of the compound o-aminodiphenylamine, gave 0.776g (51.7% yield) of a white compound having a molecular ion mass, determined by mass spectrometry, of: 768.33 (calculated value: 768.26); theoretical element content (%) C49H30F2N8: c, 76.55; h, 3.93; f, 4.94; n,14.57, measured elemental content (%): c, 76.53; h, 3.91; f, 4.58; n, 14.68. As described aboveThe analysis result shows that the obtained product is the target product.
Example 15
Figure BDA0002012591180000261
Following the synthesis of example 5, the procedure was the same, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.707g (43.9% yield) of a white compound, having a molecular ion mass determined by mass spectrometry of: 805.41 (calculated value: 805.23); theoretical element content (%) C48H27F4N9: c, 71.55; h, 3.38; f, 9.43; n,15.64, measured elemental content (%): c, 71.61; h, 3.33; f, 9.47; n, 15.66. The above analysis results show that the obtained product is the target product.
Example 16
Figure BDA0002012591180000262
Following the synthesis of example 6, following the same procedure, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 0.834g of a white compound was obtained (51.8% yield), molecular ion mass determined by mass spectrometry was: 805.19 (calculated value: 805.23); theoretical element content (%) C48H27F4N9: c, 71.55; h, 3.38; f, 9.43; n,15.64, measured elemental content (%): c, 71.66; h, 3.42; f, 9.39; n, 15.79. The above analysis results show that the obtained product is the target product.
Example 17
Figure BDA0002012591180000263
Synthesis according to example 3, the procedure is the same, the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine is used instead of the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, giving a whitish colourCompound 0.737g (45.8% yield), molecular ion mass determined by mass spectrometry: 805.31 (calculated value: 805.23); theoretical element content (%) C48H27F4N9: c, 71.55; h, 3.38; f, 9.43; n,15.64, measured elemental content (%): c, 71.70; h, 3.51; f, 9.50; n, 15.71. The above analysis results show that the obtained product is the target product.
Example 18
Figure BDA0002012591180000264
Following the synthesis of example 4, the procedure was the same, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.745g (46.3% yield) of white compound, molecular ion mass determined by mass spectrometry was: 805.17 (calculated value: 805.23); theoretical element content (%) C48H27F4N9: c, 71.55; h, 3.38; f, 9.43; n,15.64, measured elemental content (%): c, 71.39; h, 3.42; f, 9.38; n, 15.55. The above analysis results show that the obtained product is the target product.
Example 19
Figure BDA0002012591180000271
Following the synthesis of example 7, following the same procedure, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 0.523g (66.7% yield) of the white compound was obtained, the molecular ion mass determined by mass spectrometry being: 822.23 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.53; h, 3.31; f, 11.54; n, 13.62. The above analysis results show that the obtained product is the target product.
Example 20
Figure BDA0002012591180000272
Following the synthesis of example 8, the procedure was the same, substituting compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.868g (52.8% yield) of white compound, molecular ion mass determined by mass spectrometry was: 822.41 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.66; h, 3.51; f, 11.49; and N, 13.72. The above analysis results show that the obtained product is the target product.
Example 21
Figure BDA0002012591180000273
Following the synthesis of example 9, following the same procedure, the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine was used instead of the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.819g (49.8% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 822.17 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.62; h, 3.50; f, 11.47; and N, 13.59. The above analysis results show that the obtained product is the target product.
Example 22
Figure BDA0002012591180000281
Following the synthesis of example 10, the procedure was the same, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.894g (53.2% yield) of a white compound with a molecular ion mass determined by mass spectrometry of: 840.31 (calculated value: 840.22); theoretical element content (%) C49H26F6N8: c, 70.00; h, 3.12; f, 13.56; n,13.33, measured elemental content (%): c, 70.11; h, 3.08; f, 13.49; and N, 13.26. The above analysis results show that the obtained product is the target product.
Example 23
Figure BDA0002012591180000282
Following the synthesis of example 11, following the same procedure, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 0.811g (48.3% yield) of white compound was obtained, having a molecular ion mass determined by mass spectrometry of: 822.30 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.55; h, 3.30; f, 11.52; n, 13.61. The above analysis results show that the obtained product is the target product.
Example 24
Figure BDA0002012591180000283
Following the synthesis of example 12, the procedure was the same, substituting the compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.826g (49.2% yield) of a white compound, having a molecular ion mass determined by mass spectrometry of: 822.33 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.55; h, 3.42; f, 11.49; and N, 13.64. The above analysis results show that the obtained product is the target product.
Example 25
Figure BDA0002012591180000291
Synthesis according to example 13, the procedure is the sameThe compound 2-chloro-4, 6-bis (4-fluorophenyl) -1,3, 5-triazine was used instead of the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.850g (50.6% yield) of a white compound, which was determined by mass spectrometry to have a molecular ion mass of: 822.35 (calculated value: 822.23); theoretical element content (%) C49H27F5N8: c, 71.53; h, 3.31; f, 11.54; n,13.62, measured elemental content (%): c, 71.60; h, 3.41; f, 11.59; n, 13.54. The above analysis results show that the obtained product is the target product.
Example 26
Figure BDA0002012591180000292
Synthesis according to example 2, the same procedure was followed, using Compound N1- (3- (3-pyridyl) phenyl) -1, 2-phenylenediamine, instead of the compound o-aminodiphenylamine, gives 0.889g (yield 54.9%) of a white compound having a molecular ion mass determined by mass spectrometry of: 809.25 (calculated value: 809.30); theoretical element content (%) C54H35N9: c, 80.08; h, 4.36; n,15.56, measured elemental content (%): c, 80.18; h, 4.46; n, 15.66. The above analysis results show that the obtained product is the target product.
Example 27
Figure BDA0002012591180000293
5.87g (22.0mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 2.44g (10.0mmol) of 5-bromo-1, 3-benzenediboronic acid, 3.45g (25.0mmol) of potassium carbonate were charged into a 250mL two-necked flask, 100mL of THF, H2O13 mL, adding 100mg of catalyst tetrakis (triphenylphosphine) palladium under nitrogen, and refluxing for 24 h. The reaction mixture was washed with dichloromethane/water, and the organic phase was subjected to solvent removal and column chromatography to obtain compound a as a white solid, 1.83g (yield 29.6%).
15mL of water dissolved NaHSO33.12g (30mmol), 730mg (2.00mmol) of benzaldehyde was added, and the mixture was stirred at room temperature for 5 hours. Then adding N1- (4-bromophenyl)) 524mg (2mmol) of 1, 2-phenylenediamine is added with 30mL of ethanol and refluxed for 24h under the protection of nitrogen. After cooling to room temperature, filtration was carried out to obtain a white crude product B.
The crude product B (0.696g, 2.00mmol), pinacol diborate 1.02g (4.00mmol), dried potassium acetate 1.96g (20.0mmol), and dried 1, 4-dioxane 120mL were placed in a 250mL two-necked flask, and the catalyst [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium 150mg (0.20mmol) was added under nitrogen protection, and refluxed for 24 h. After cooling to room temperature, potassium acetate was removed by filtration, dioxane was removed from the filtrate, and the filtrate was washed with dichloromethane/water, and the organic phase was freed from the organic solvent and subjected to column chromatography using dichloromethane as a developing solvent to give a white solid intermediate C, 745 mg.
The above white intermediate A (649mg, 1.05mmol), intermediate C (348mg, 1.00mmol), potassium carbonate 207mg (1.5mmol) were charged into a 100mL two-necked flask, and THF 25mL, H was added2O1 mL, adding catalyst tetrakis (triphenylphosphine) palladium 25.0mg under nitrogen, and refluxing for 12 h. The reaction mixture was washed with dichloromethane/water, and the organic phase was subjected to solvent removal and column chromatography to obtain 509mg (yield 63.2%) of a white solid compound. The mass of the molecular ions determined by mass spectrometry was: 808.12 (calculated value: 808.31); theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.76; h, 4.50; and N, 13.89. The above analysis results show that the obtained product is the target product.
Example 28
Figure BDA0002012591180000301
Synthesis according to example 10, the same procedure was followed, using Compound N1- (2-bromophenyl) -1, 2-phenylenediamine instead of Compound N1- (4-bromophenyl) -1, 2-phenylenediamine, to give a white compound 0.438g (54.2% yield) having a molecular ion mass of 808.32 (calculated: 808.31) as determined by mass spectrometry; theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.72; h, 4.53; n,13.79. The above analysis results show that the obtained product is the target product.
Example 29
Figure BDA0002012591180000302
Synthesis according to example 10, the same procedure was followed, using Compound N1- (3-bromophenyl) -1, 2-phenylenediamine instead of Compound N1- (4-bromophenyl) -1, 2-phenylenediamine, to give a white compound of 0.427g (52.9% yield) and a molecular ion mass of 808.38 (calculated: 808.31) as determined by mass spectrometry; theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.62; h, 4.43; and N, 13.99. The above analysis results show that the obtained product is the target product.
Example 30
Figure BDA0002012591180000311
5.87g (22.0mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 2.44g (10.0mmol) of 5-bromo-1, 3-benzenediboronic acid, 3.45g (25.0mmol) of potassium carbonate were charged into a 250mL two-necked flask, 100mL of THF, H2O13 mL, adding 100mg of catalyst tetrakis (triphenylphosphine) palladium under nitrogen, and refluxing for 24 h. The reaction mixture was washed with dichloromethane/water, and the organic phase was subjected to solvent removal and column chromatography to obtain compound a (1.83g, yield 29.6%) as a white solid.
The above white intermediate A (522mg, 1.50mmol), 248mg (1.65mmol) of 3-formylphenylboronic acid and 455mg (3.3mmol) of potassium carbonate were put into a 100mL two-necked flask, and THF 25mL, H was added2O1.5 mL, under nitrogen, add catalyst tetrakis (triphenylphosphine) palladium 25.0mg, reflux 12 h. Washing the reaction solution with dichloromethane/water, removing the solvent from the organic phase by rotary column chromatography, and purifying by column chromatography to obtain a white solid compound D, 900 mg.
5mL of water dissolved NaHSO3(1.56g, 15.0mmol), intermediate D (0.644g, 1.00mmol) was added and stirred at ambient temperature for 5 h. Then adding o-aminodiphenyl0.193g (1.05mmol) of amine, 20mL of ethanol are added and the mixture is refluxed for 12h under the protection of nitrogen. After cooling to room temperature, filtration was carried out to obtain a white crude product. Column chromatography with dichloromethane afforded 0.721g (89.2% yield) of the product as a white solid. The mass of the molecular ions determined by mass spectrometry was: 808.28 (calculated value: 808.31); theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.63; h, 4.45; and N, 13.89. The above analysis results show that the obtained product is the target product.
Example 31
Figure BDA0002012591180000312
Synthesis according to example 30, following the same procedure, substituting compound 4-formylphenylboronic acid for compound 3-formylphenylboronic acid, gave 0.675g (83.5% yield) of a white compound having a molecular ion mass of 808.42 (calculated: 808.31) as determined by mass spectrometry; theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.63; h, 4.53; n, 13.88. The above analysis results show that the obtained product is the target product.
Example 32
Figure BDA0002012591180000321
Synthesis according to example 30, following the same procedure, substituting compound 2-formylphenylboronic acid for compound 3-formylphenylboronic acid, gave 0.728g (90.1% yield) of the white compound having a molecular ion mass of 808.32 (calculated: 808.31) as determined by mass spectrometry; theoretical element content (%) C55H36N8: c, 81.66; h, 4.49; n, 13.85; measured elemental content (%): c, 81.58; h, 4.46; and N, 13.87. The above analysis results show that the obtained product is the target product.
Example 33
Figure BDA0002012591180000322
The synthesis according to example 1, following the same procedure, substituting the compound benzaldehyde with the compound 3-trifluoromethylbenzaldehyde, gave 0.625g (52.1% yield) of a white compound with a mass of molecular ions determined by mass spectrometry of: 800.23 (calculated: 800.26); theoretical element content (%) C50H31F3N8: c, 74.99; h, 3.90; f, 7.12; n,13.99, measured elemental content (%): c, 75.05; h, 3.94; f, 7.02; and N, 13.99. The above analysis results show that the obtained product is the target product.
Example 34
Figure BDA0002012591180000323
Following the synthesis of example 1, following the same procedure, compound 3, 5-bis (trifluoromethyl) benzaldehyde was used instead of compound benzaldehyde to give 0.432g (33.2% yield) of a white compound with a mass spectrometrically determined molecular ion mass of: 868.22 (calculated value: 868.25); theoretical element content (%) C51H30F6N8: c, 70.50; h, 3.48; f, 13.12; n,12.90, measured elemental content (%): c, 70.52; h, 3.50; f, 13.17; n, 12.92. The above analysis results show that the obtained product is the target product.
Example 35
Figure BDA0002012591180000324
Following the synthesis of example 2, following the same procedure, the compound N- (3-trifluoromethylphenyl) -1, 2-phenylenediamine was used instead of the compound o-aminodiphenylamine to give 0.622g (51.8% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 800.29 (calculated value: 800.26); theoretical element content (%) C50H31F3N8: c, 74.99; h, 3.90; f, 7.12; n,13.99, measured elemental content (%): c, 75.00; h, 3.92; f, 7.09;n, 13.92. The above analysis results show that the obtained product is the target product.
Example 36
Figure BDA0002012591180000331
Following the synthesis of example 2, following the same procedure, the compound N- (3, 5-bis (trifluoromethyl) phenyl) -1, 2-phenylenediamine was used instead of the compound o-aminodiphenylamine to give 0.675g (51.8% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 868.27 (calculated value: 868.25); theoretical element content (%) C51H30F6N8: c, 70.50; h, 3.48; f, 13.12; n,12.90, measured elemental content (%): c, 70.44; h, 3.46; f, 13.19; n, 12.98. The above analysis results show that the obtained product is the target product.
Example 37
Figure BDA0002012591180000332
Following the synthesis of example 3, the procedure was the same, substituting the compound 2-chloro-4, 6-bis (4-trifluoromethylphenyl) -1,3, 5-triazine for the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 0.657g (43.6% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 1005.22 (calculated: 1005.22); theoretical element content (%) C52H27F12N9: c, 62.10; h, 2.71; f, 22.67; n,12.53, measured elemental content (%): c, 62.13; h, 2.72; f, 22.66; n, 12.55. The above analysis results show that the obtained product is the target product.
Example 38
Figure BDA0002012591180000333
The synthesis according to example 7, procedure is the same, the compound 2-chloro-4, 6-bis (4-trifluoromethylphenyl) -1,3, 5-triazine is used instead of the compound 2-chloro-4, 6-diphenyl-1,3, 5-triazine, replacing compound 3-fluorobenzaldehyde with compound 3-trifluoromethylbenzaldehyde to give 0.847g (52.7% yield) of a white compound with a mass spectrometrically determined mass of the molecular ion: 1072.25 (calculated value: 1072.21); theoretical element content (%) C54H27F15N8: c, 60.46; h, 2.54; f, 26.56; n,10.44, measured elemental content (%): c, 60.49; h, 2.53; f, 26.55; n, 10.52. The above analysis results show that the obtained product is the target product.
Example 39
Figure BDA0002012591180000341
Following the synthesis of example 10, following the same procedure, the compound 2-chloro-4, 6-bis (4-trifluoromethylphenyl) -1,3, 5-triazine was used instead of the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and the compound 3, 5-bis (trifluoromethyl) benzaldehyde was used instead of the compound 3, 5-difluorobenzaldehyde, giving 0.869g (50.8% yield) of the white compound with a mass of molecular ions determined by mass spectrometry: 1140.23 (calculated value: 1140.20); theoretical element content (%) C55H26F18N8: c, 57.91; h, 2.30; f, 29.98; n,9.82, measured elemental content (%): c,57.93, 2.33; f, 29.95; and N, 9.95. The above analysis results show that the obtained product is the target product.
Example 40
Figure BDA0002012591180000342
According to the synthesis of example 12, following the same procedure, the compound 2-chloro-4, 6-bis (4-trifluoromethylphenyl) -1,3, 5-triazine was used instead of the compound 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and N- (3-trifluoromethylphenyl) -1, 2-phenylenediamine instead of the compound N- (3-fluorophenyl) -1, 2-phenylenediamine, giving 0.791g (49.2% yield) of a white compound having a molecular ion mass determined by mass spectrometry of: 1072.28 (calculated value: 1072.21); theoretical element content (%) C54H27F15N8：C,60.46；H, 2.54; f, 26.56; n,10.44, measured elemental content (%): c, 60.52; h, 2.56; f, 26.58; n, 10.38. The above analysis results show that the obtained product is the target product.
EXAMPLE 41
Figure BDA0002012591180000343
The synthesis of example 7 was performed in the same manner and using compound 2-isopropylbenzaldehyde instead of compound 2-fluorobenzaldehyde to obtain 0.535g (26.4% yield) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 774.31 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 42
Figure BDA0002012591180000351
According to the synthesis of example 8, using the same procedure, compound 3-isopropylbenzaldehyde was used instead of compound 3-fluorobenzaldehyde, to obtain 0.514g (yield 27.4%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 774.34 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 43
Figure BDA0002012591180000352
According to the synthesis of example 9, using the same procedure, compound 4-isopropylbenzaldehyde was used instead of compound 4-fluorobenzaldehyde, to obtain 0.535g (yield 26.4%) of a white compound. The mass of the molecular ions determined by mass spectrometry was:774.31 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 44
Figure BDA0002012591180000353
According to the synthesis of example 10, same procedure was used to replace the compound 3, 5-difluorobenzaldehyde by the compound 3, 5-diisopropylbenzaldehyde to obtain 0.549g (yield 22.3%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 816.30 (calculated value: 816.37); theoretical element content (%) C55H44N8: c, 80.86; h, 5.43; n, 13.72; measured elemental content (%): c, 80.84; h, 5.47; n, 13.69. The above analysis results show that the obtained product is the target product.
Example 45
Figure BDA0002012591180000361
Synthesis according to example 11, the procedure is the same, using Compound N1- (2-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1- (2-fluorophenyl) benzene-1, 2-diamine to give 0.515g (yield 25.4%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 774.37 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 46
Figure BDA0002012591180000362
Synthesis according to example 12, the procedure is the sameWith compounds N1- (3-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1- (3-fluorophenyl) benzene-1, 2-diamine to give 0.510g (yield 25.9%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 774.34 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 47
Figure BDA0002012591180000363
Synthesis according to example 13, the same procedure was followed, using Compound N1- (4-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1- (4-fluorophenyl) benzene-1, 2-diamine to give 0.515g (yield 25.4%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 774.37 (calculated value: 774.32); theoretical element content (%) C52H38N8: c, 80.60; h, 4.94; n, 14.46; measured elemental content (%): c, 80.64; h, 4.97; n, 14.39. The above analysis results show that the obtained product is the target product.
Example 48
Figure BDA0002012591180000371
Synthesis according to example 14, the procedure is the same, using Compound N1- (3, 5-diisopropylphenyl) benzene-1, 2-diamine instead of Compound N1- (3, 5-fluorophenyl) benzene-1, 2-diamine to give 0.529g of a white compound (yield 27.2%). The mass of the molecular ions determined by mass spectrometry was: 816.30 (calculated value: 816.37); theoretical element content (%) C55H44N8: c, 80.86; h, 5.43; n, 13.72; measured elemental content (%): c, 80.84; h, 5.47; n, 13.69. The above analysis results show that the obtained product is the target product.
Example 49
Figure BDA0002012591180000372
According to the synthesis of example 27, using the same procedure, compound benzaldehyde was replaced with compound 3-isopropylbenzaldehyde to obtain 0.523g (yield 37.9%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 850.36 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.91; and N, 13.24. The above analysis results show that the obtained product is the target product.
Example 50
Figure BDA0002012591180000373
According to the synthesis of example 28, using the same procedure, compound benzaldehyde was replaced with compound 3-isopropylbenzaldehyde to obtain 0.503g (37.6% yield) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 850.38 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.91; and N, 13.24. The above analysis results show that the obtained product is the target product.
Example 51
Figure BDA0002012591180000381
According to the synthesis of example 29, using the same procedure, compound benzaldehyde was replaced with compound 3-isopropylbenzaldehyde to obtain 0.501g (yield 37.6%) of a white compound. The mass of the molecular ions determined by mass spectrometry was: 850.39 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.91; and N, 13.24. The above analysis results show thatThe product of (a) is a target product.
Example 52
Figure BDA0002012591180000382
Synthesis according to example 30, the procedure is the same, using Compound N1- (3-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1Phenyl-1, 2-diamine, 0.520g of white compound was obtained (yield 34.9%). The mass of the molecular ions determined by mass spectrometry was: 850.34 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.91; and N, 13.24. The above analysis results show that the obtained product is the target product.
Example 53
Figure BDA0002012591180000383
Synthesis according to example 31, the procedure is the same, starting with Compound N1- (4-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1Phenyl-1, 2-diamine, 0.503g of white compound was obtained (yield 23.9%). The mass of the molecular ions determined by mass spectrometry was: 850.37 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.91; and N, 13.24. The above analysis results show that the obtained product is the target product.
Example 54
Figure BDA0002012591180000391
Synthesis according to example 32, the procedure is the same, using Compound N1- (4-isopropylphenyl) benzene-1, 2-diamine in place of Compound N1Phenyl-1, 2-diamine, 0.523g of white compound was obtained (37.9% yield). Mass spectrometric analysis of determined moleculesThe ion mass is: 850.31 (calculated value: 850.35); theoretical element content (%) C58H42N8: c, 81.86; h, 4.97; n, 13.17; measured elemental content (%): c, 81.85; h, 4.92; n, 13.23. The above analysis results show that the obtained product is the target product.
Example 55
Figure BDA0002012591180000392
According to the synthesis of example 27, using the same procedure, compound 2-methylbenzaldehyde was used instead of compound benzaldehyde, and 0.538g of a white compound was obtained (yield 39.9%). The mass of the molecular ions determined by mass spectrometry was: 822.34 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.75; h, 4.61; and N, 13.64. The above analysis results show that the obtained product is the target product.
Example 56
Figure BDA0002012591180000393
According to the synthesis of example 28, using the same procedure, compound 3-methylbenzaldehyde was used instead of compound benzaldehyde, and 0.614g of a white compound was obtained (yield 37.4%). The mass of the molecular ions determined by mass spectrometry was: 822.38 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.79; h, 4.60; n, 13.61. The above analysis results show that the obtained product is the target product.
Example 57
Figure BDA0002012591180000401
Synthesis of the same procedure as in example 29, using 3-methylbenzaldehyde as the compound instead of benzaldehyde as the compound, givingTo 0.523g of white compound (37.9% yield). The mass of the molecular ions determined by mass spectrometry was: 822.38 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.78; h, 4.61; n, 13.61. The above analysis results show that the obtained product is the target product.
Example 58
Figure BDA0002012591180000402
Synthesis according to example 30, the procedure is the same, using Compound N1- (p-tolyl) benzene-1, 2-diamine in place of Compound N1-phenyl-1, 2-diamine to give 0.598g of white compound (37.2% yield). The mass of the molecular ions determined by mass spectrometry was: 822.39 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.78; h, 4.62; and N, 13.60. The above analysis results show that the obtained product is the target product.
Example 59
Figure BDA0002012591180000403
Synthesis according to example 31, the procedure is the same, starting with Compound N1- (p-tolyl) benzene-1, 2-diamine in place of Compound N1Phenyl-1, 2-diamine, 0.523g of white compound was obtained (37.9% yield). The mass of the molecular ions determined by mass spectrometry was: 822.36 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.78; h, 4.61; n, 13.61. The above analysis results show that the obtained product is the target product.
Example 60
Figure BDA0002012591180000411
Synthesis according to example 32, the procedure is the same, using Compound N1- (m-tolyl) benzene-1, 2-diamine in place of Compound N1Phenyl-1, 2-diamine, 0.510g of white compound was obtained (yield 35.9%). The mass of the molecular ions determined by mass spectrometry was: 822.36 (calculated value: 822.32); theoretical element content (%) C56H38N8: c, 81.73; h, 4.65; n, 13.62; measured elemental content (%): c, 81.78; h, 4.61; n, 13.61. The above analysis results show that the obtained product is the target product.
Effect example 1
The following embodiments of the electroluminescent device prepared by using the material of the present invention have the following specific device preparation processes: the transparent ITO glass is used as a substrate material for preparing a device, ultrasonic treatment is carried out for 30min by using 5% ITO washing liquor, then ultrasonic washing is carried out by using distilled water (2 times), acetone (2 times) and isopropanol (2 times) in sequence, and finally the ITO glass is stored in the isopropanol. Before each use, the surface of the ITO glass is carefully wiped by using an acetone cotton ball and an isopropanol cotton ball, and after the ITO glass is washed by isopropanol and dried, the ITO glass is treated by plasma for 5 min. The preparation of the device is completed by vacuum evaporation process by using vacuum coating equipment, and when the vacuum degree of a vacuum evaporation system reaches 5 multiplied by 10-4And (3) starting evaporation at a deposition rate of less than Pa, and sequentially depositing various organic layers, a LiF electron injection layer and a metal Al electrode on the ITO glass by using a vacuum evaporation process from a Saynes film thickness instrument (the specific device structure is shown in the following effect examples). The characteristics of the device such as current, voltage, brightness, light-emitting spectrum and the like are synchronously tested by a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed in a water-free and oxygen-free glove box.
Effect examples 1-1 to 60-1 in the organic electroluminescent devices, HATCN was used as a hole injecting layer, DBBA as a 1 st hole transporting layer, TCTA as a 2 nd hole transporting layer, TCTA in the light emitting layer was mixed with the compounds 1 to 60 of the present invention respectively and used as a host material (the weight mixing ratio of TCTA to the compounds 1 to 60 was 1:1), and the compounds 1 to 60 of the present invention were used as an electric materialThe sub-transmission material is used. Effect example the organic electroluminescent device has a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA: n +10wt％IrPPy3/n(30nm)/LiF(1nm)/Al(100nm)]. n represents the compound number: 1-60, the compound used in the main body material and the compound used in the electron transport layer in the same device are the same, IrPPy3Used as a doped luminescent material (the weight ratio doping concentration is 10)WT%). Effect examples the results are shown in table 1-1.
Comparative example 1
Comparative examples 1-1 to 3-1 organic electroluminescent devices in which HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; TCTA is mixed with 3P-T2T, E1 or E2 as a host material in the luminescent layer, the two materials are mixed according to the weight ratio of 1:1, IrPPy3Doped luminescent material (weight ratio doping concentration of 10)WT%), 3P-T2T, E1 or E2 were used simultaneously as electron transport materials. Comparative examples 1-1 to 3-1 the organic electroluminescent device had a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA:3P-T2T or E1 or E2+10 wt% IrPPy3/3P-T2T or E1 or E2(30nm)/LiF (1nm)/Al (100nm)]。
Comparative examples 4-1 to 16-1 devices, HATCN was used as the hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; comparative examples 4-1 to 16-1 devices TBT-07, TBT-14, ET85, 1,2, 3,4, 40, 45, 47, 50, 55 and 60 were used as Electron Transport Layer (ETL) materials and as host materials in the light emitting layer, respectively. Comparative examples 4-1 to 16-1 organic electroluminescent device having a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/n +10 wt% IrPPy3/n(30nm)/LiF(1nm)/Al(100nm)]. n represents the number of the compound, the compound adopted in the main body material in the same device is the same as the compound adopted in the electron transport layer, IrPPy3Used as a doped luminescent material (the weight ratio doping concentration is 10)WT%). The results of the comparative examples are shown in Table 2-1.
The structures of the compounds referred to in the effect examples and comparative examples are as follows:
Figure BDA0002012591180000421
TABLE 1-1. example devices at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000422
Figure BDA0002012591180000431
Figure BDA0002012591180000441
TABLE 2-1. devices of comparative examples at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000442
Figure BDA0002012591180000451
As can be seen from the above effects of example 1 and tables 1-1, the luminance of the organic electroluminescent device prepared by using the 1,3, 5-triazine compound of the present invention as an electron transport layer and simultaneously as an electron acceptor material and an electron donor material to construct a light emitting layer can reach 8315cd/m2-8898cd/m2(ii) a The current efficiency can reach 80cd/A-91 cd/A; the service life of the device can reach 1078 hours to 1300 hours (T90)
As is clear from the comparative example 1 and Table 2-1, the luminance of the organic electroluminescent device obtained by constructing the light-emitting layer using the above-mentioned compound as the electron transporting layer and as the electron acceptor material was 5082cd/m2-5743cd/m2(ii) a The current efficiency is 50cd/A-61 cd/A; the device lifetime ranged from 410 hours to 689 hours (T90).
Therefore, compared with the organic electroluminescent device prepared by using the compound as the electron transport layer and simultaneously as the electron acceptor material and the electron donor material to construct the luminescent layer, the brightness of the organic electroluminescent device prepared by using the 1,3, 5-triazine compound as the electron transport layer and simultaneously as the electron acceptor material to construct the luminescent layer is improved by 45-75 percent, and the current efficiency is improved by 31-82 percent; the service life of the device is improved by 56.5-217%.
Effect example 2
In the organic electroluminescent devices of effect examples 1-2 to 60-2, HATCN was used as a hole injection layer, DBBA was used as a 1 st hole transport layer, TCTA was used as a 2 nd hole transport layer, TCTA was mixed with the compounds 1 to 60 in the present invention in the light emitting layer respectively as a host material (the weight mixing ratio of TCTA to the compounds 1 to 60 was 1:1), and TPBI was used as an electron transport material. Effect example the organic electroluminescent device has a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA: n +10wt％IrPPy3/TPBI(30nm)/LiF(1nm)/Al(100nm)]. n represents the compound number: 1-60, the compound used in the main body material and the compound used in the electron transport layer in the same device are the same, IrPPy3Used as a doped luminescent material (the weight ratio doping concentration is 10)WT%). Effect examples the results are shown in tables 1-2.
Comparative example 2
Comparative examples 1-2 to 6-2 organic electroluminescent devices, HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; TCTA is mixed with one of 3P-T2T, E1, E2, TBT-07, TBT-14 and ET85 as a host material in the luminescent layer, and the two materials are mixed according to the weight ratio of 1:1，IrPPy3Doped luminescent material (weight ratio doping concentration of 10)WT%), TPBI was used as the electron transport material. Comparative examples 1-2 to 6-2 organic electroluminescent devices having a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA 3P-T2T, E1, E2, TBT-07, TBT-14 or ET85+10 wt% IrPPy3/TPBI(30nm)/LiF(1nm)/Al(100nm)]。
Comparative examples 7-2 to 16-2 devices in which HATCN was used as the hole injecting layer, DBBA was used as the 1 st hole transporting layer, TCTA was used as the 2 nd hole transporting layer, compounds 1,2, 3,4, 40, 45, 47, 50, 55 and 60 were used as host materials in the light emitting layer, IrPPy3Is used as a doped luminescent material (with a weight ratio doping concentration of 10)WT%); TPBI is used as an electron transport material. Comparative examples 7-2 to 15-2 organic electroluminescent device having a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/n +10 wt% IrPPy3/TPBI(30nm)/LiF(1nm)/Al(100nm)]. The results of the comparative examples are shown in Table 2-2.
TABLE 1-2. example devices at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000461
Figure BDA0002012591180000471
Figure BDA0002012591180000481
TABLE 2-2. devices of comparative examples at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000482
As can be seen from the above effect example 2 and tables 1-2, the luminance of the organic electroluminescent device prepared by using the 1,3, 5-triazine compound of the present invention as a composition of the electron acceptor material and the electron donor material to construct the light-emitting layer can reach 7156cd/m2-7890cd/m2(ii) a The current efficiency can reach 70cd/A-80 cd/A; the device lifetime can reach 841 hours to 980 hours (T90).
As is clear from the above comparative example 2 and tables 2 to 2, the luminance of the organic electroluminescent device prepared by constructing the light-emitting layer using the above compound was 5046cd/m2-5715cd/m2(ii) a The current efficiency is 45cd/A-63 cd/A; the device lifetime ranged from 410 hours to 672 hours (T90).
Therefore, compared with the organic electroluminescent device prepared by the luminescent layer constructed by the compound, the organic electroluminescent device prepared by adopting the 1,3, 5-triazine compound as the electron acceptor material and the electron donor material to construct the luminescent layer has the advantages that the brightness is improved by 25-56%, and the current efficiency is improved by 11-78%; the service life of the device is improved by 25-139%.
Effect example 3
In the organic electroluminescent devices of effect examples 1-3 to 60-3, HATCN was used as the hole injection layer, DBBA was used as the 1 st hole transport layer, TCTA was used as the 2 nd hole transport layer, TCTA was used as the host material in the light-emitting layer, and compounds 1 to 60 were used as the electron transport materials, respectively. Effect example the organic electroluminescent device has a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA +10wt％IrPPy3/n(30nm)/LiF(1nm)/Al(100nm)]. n represents the compound number: 1-60, the compound used in the main body material and the compound used in the electron transport layer in the same device are the same, IrPPy3Used as a doped luminescent material (the weight ratio doping concentration is 10)WT%). Effect examples the results are shown in tables 1-3.
Comparative example 3
Comparative examples 1-3 to 6-3 organic electroluminescent devices, HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; in the light-emitting layer TCTA as host material, IrPPy3Doped luminescent material (weight ratio doping concentration of 10)WT%) 3P-T2T, E1, E2, TBT-07, TBT-14 and ET85 were used as electron transport materials, respectively. Comparative examples 1-3 to 6-3 the organic electroluminescent device had a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA +10 wt% IrPPy3/3P-T2T, E1, E2, TBT-07, TBT-14 or ET85(30nm)/LiF (1nm)/Al (100nm)]. The results of the comparative examples are shown in tables 2 to 3.
Tables 1-3. example devices at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000491
Figure BDA0002012591180000501
Figure BDA0002012591180000511
Tables 2-3. devices of comparative examples at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000512
As is clear from the above effects of example 3 and tables 1 to 3, the organic electroluminescent element produced by using the 1,3, 5-triazine compound of the present invention as an electron transport layer has a high luminanceUp to 6379cd/m2-7068cd/m2(ii) a The current efficiency can reach 65cd/A-85 cd/A; the device lifetime can reach 791-878 hours (T90).
As is clear from the above comparative example 3 and tables 2 to 3, the luminance of the organic electroluminescent device prepared by using the compound of the above comparative example as an electron transporting layer was 4862cd/m2-5196cd/m2(ii) a The current efficiency is 50cd/A-56 cd/A; the device lifetime ranged from 361 hours to 496 hours (T90).
Therefore, compared with the existing compound, the brightness of the organic electroluminescent device prepared by the 1,3, 5-triazine compound as an electron transport layer is improved by 22.8-45%, and the current efficiency is improved by 16-70%; the service life of the device is improved by 60-143%.
Effect example 4
In the organic electroluminescent devices of effect examples 1-4 to 60-4, HATCN was used as a hole injection layer, DBBA was used as a 1 st hole transport layer, TCTA was used as a 2 nd hole transport layer, TCTA was mixed with the compounds 1 to 60 of the present invention in the light emitting layer respectively as a host material (the weight mixing ratio of TCTA to the compounds 1 to 60 was 1:1), and the compounds 1 to 60 of the present invention were used as an electron transport material. Effect example the organic electroluminescent device has a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA: n +1wt％DPh2AAN/n(30nm)/LiF(1nm)/Al(100nm)]. n represents the compound number: 1-60, the compound adopted in the main body material in the same device is the same as that adopted in the electron transport layer, and DPh2AAN is used as a doped luminescent material (the weight ratio doping concentration is 1)WT%). Effect examples the results are shown in tables 1 to 5.
Comparative example 4
Comparative examples 1-4 to 3-4 organic electroluminescent devices, HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; TCTA is mixed with 3P-T2T, E1 or E2 respectively as a host material in the luminescent layer, the two materials are mixed according to the weight ratio of 1:1, and a DPh2AAN doped luminescent material is used (the weight ratio of the doping concentration is equal to that of the luminescent material)1WT%) 3P-T2T, E1 or E2 were used as electron transport materials, respectively. Comparative examples 1-1 to 3-1 organic electroluminescent device having a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA:3P-T2T or E1 or E2+10 wt% DPh2AAN/3P-T2T or E1 or E2(30nm)/LiF (1nm)/Al (100nm)]。
Tables 1-4. example devices at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000521
Figure BDA0002012591180000531
Figure BDA0002012591180000541
Tables 2-4. devices of comparative examples at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000542
As can be seen from the effect examples and tables 1 to 4, the luminance of the organic electroluminescent device prepared by using the 1,3, 5-triazine compound as an electron transport layer and simultaneously as an electron acceptor material and an electron donor material to construct a luminescent layer can reach 3531cd/m2-3885cd/m2(ii) a The current efficiency can reach 54cd/A-62 cd/A; the device lifetime can reach 914 hours to 987 hours (T90).
As can be seen from the comparative examples and tables 2 to 4, the light emitting layer was fabricated using the above-mentioned compound as an electron transporting layer and an electron acceptor materialThe luminance of the organic electroluminescent device was 2350cd/m2-2571cd/m2(ii) a The current efficiency is 39cd/A-41 cd/A; the device lifetime ranged from 402 hours to 462 hours (T90).
Therefore, compared with the organic electroluminescent device prepared by using the compound as the electron transport layer and simultaneously as the electron acceptor material and the electron donor material to construct the luminescent layer, the brightness of the organic electroluminescent device prepared by using the 1,3, 5-triazine compound as the electron transport layer and simultaneously as the electron acceptor material to construct the luminescent layer is improved by 37-65%, and the current efficiency is improved by 31-59%; the service life of the device is improved by 98-146%.
Effect example 5
In the organic electroluminescent devices of effect examples 1-5 to 60-5, HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, TCTA was used as the 2 nd hole transport layer, TCTA was mixed with the compounds 1 to 60 in the present invention in the light emitting layer respectively as a host material (the weight mixing ratio of TCTA to the compounds 1 to 60 was 1:1), and TPBI was used as an electron transport material. Effect example the organic electroluminescent device has a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA: n +1wt％DPh2AAN/TPBI(30nm)/LiF(1nm)/Al(100nm)]. n represents the compound number: 1-60, DPh2AAN is used as a doped luminescent material (the weight ratio doping concentration is 1)WT%). Effect examples the results are shown in tables 1 to 5.
Comparative example 5
Comparative examples 1-5 to 3-5 organic electroluminescent devices, HATCN was used as a hole injection layer, DBBA was used as the 1 st hole transport layer, and TCTA was used as the 2 nd hole transport layer; TCTA is mixed with 3P-T2T, E1 or E2 respectively as a host material in the luminescent layer, the two materials are mixed according to the weight ratio of 1:1, and a DPh2AAN doped luminescent material is used (the weight ratio doping concentration is 1)WT%), TPBI was used as the electron transport material. Comparative examples 1-5 to 3-5 organic electroluminescent device having a structure of [ ITO/HATCN (5nm)/DBBA (60nm)/TCTA (10nm)/TCTA:3P-T2T or E1 or E2+10 wt% DPh2AAN/TPBI (30nm)/LiF (1nm)/Al (100nm) ]]。
Tables 1-5. example devices at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000551
Figure BDA0002012591180000561
Figure BDA0002012591180000571
Tables 2-5. comparative example device at a drive current density of 10mA/cm2Test data (device lifetime T90 represents the time it takes for the device luminance to decay to 90% of the initial luminance) under the conditions (constant current driving mode).
Figure BDA0002012591180000572
As can be seen from the effect examples and tables 1 to 5, the luminance of the organic electroluminescent device prepared by adopting the 1,3, 5-triazine compound as the electron acceptor material and the electron donor material to construct the luminescent layer can reach 3251cd/m2-3594cd/m2(ii) a The current efficiency can reach 48cd/A-56 cd/A; the device lifetime can reach 650 hours-748 hours (T90).
As can be seen from the comparative example and tables 2 to 5, the luminance of the organic electroluminescent device prepared by constructing the light-emitting layer using the above compound as the electron acceptor material was 2032cd/m2-2205cd/m2(ii) a The current efficiency is 34cd/A-38 cd/A; the device lifetime ranged from 342 hours to 375 hours (T90).
Therefore, compared with the existing compounds, the 1,3, 5-triazine compound is used as an electron acceptor material to construct an organic electroluminescent device prepared by a luminescent layer, the brightness is improved by 47-77%, and the current efficiency is improved by 26-65%; the service life of the device is improved by 73-119%.
The 1,3, 5-triazine compound shown in the formula I has a parent nucleus which is a benzene ring and is linked with two triazines and one benzimidazole derivative through a single bond, and the molecular structure is very complex and mainly represented as follows: (1) two triazine heterocycles and one benzimidazole heterocycle form a complex compound heterocyclic ring system; (2) two triazine derivatives and one benzimidazole derivative are linked at the periphery of a benzene ring through a single bond, and the molecular conformation structure of the molecule is very complex; (3) triazine derivatives and benzimidazole derivatives belong to electron-deficient groups, and triazine derivatives have stronger electron-deficient characteristics than benzimidazole derivatives, so that the molecules have certain intramolecular charge transfer characteristics. Based on the three characteristics, the basic electroluminescent characteristics of a molecule based on two triazines and one benzimidazole cannot be predicted or judged according to the existing physicochemical knowledge, because the three characteristics have important influence on the electroluminescent performance (mainly comprising efficiency and stability) of one material. Therefore, the judgment of the electroluminescent properties of these materials must be made by experimental verification of practical embodiments.
It is well known to those skilled in the art of organic electroluminescent materials and devices that a good electron transport material may not necessarily be a good host material. As a good host material, it should generally have balanced and good electron and hole transport properties. However, the properties of the host material also depend on the carrier transport characteristics of the doped luminescent material matched thereto and of the doped thin film as a whole after doping. For example, a host material with electron transport dominance may be well matched with a dopant material with a certain hole transport ability, and a poor result may be obtained by matching a dopant material with a certain electron transport ability. It should be noted that the carrier transport performance of the composite film obtained after host/guest doping is not always the simple superposition of the two individual performances, the carrier transport performance of the doped composite film is difficult to accurately guess, and an ideal matching combination can be obtained by a specific experimental analysis and verification method. In addition, the main body material composed of two components of an electron donor and an electron acceptor is more complicated, and the performance of the main body material is difficult to accurately infer by experience.
For example, as is apparent from tables 2-1, 2-2 and 3-2 above, the efficiency and lifetime of the organic electroluminescent device prepared using the conventional compounds E1, E2 or 3P-T2T as both an electron transporting material and a light-emitting layer host material, or as only one of light-emitting layer host materials, are not significantly improved as compared with the case where they are used only as an electron transporting material.
While CN102593374B discloses compound TPT-07 as an electron transport layer, or as an electron transport layer together with, as a host material for the preparation of electroluminescent devices. However, the efficiency of the resulting light emitting device is still low.
According to the comparison of the performance indexes of the effect examples and the comparative examples, when the compound of the invention is used as a composition of an electron acceptor material and an electron donor material and is used as a main material of a light-emitting layer, the brightness, the efficiency and the service life of the prepared organic electroluminescent device are obviously higher than those of the materials disclosed in the prior art under the same driving current density; furthermore, when the compound provided by the invention is used as an electron transport layer and is simultaneously used as an electron acceptor material and an electron donor material to construct a light-emitting layer, the organic electroluminescent device prepared under the same driving current density can obtain better brightness, efficiency and service life. Especially, the stability of the device has the most obvious technical effect advantage.

Claims (20)

1. A1, 3, 5-triazine compound shown in formula I,
Figure FDA0003230989820000011
wherein L is a single bond or
Figure FDA0003230989820000012
Ring A is phenyl, substituted by one or more Rd-1Substituted phenyl; when R isd-1Independently a plurality of the same or different;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22and R23Independently hydrogen, deuterium, halogen, cyano, C1～C6Alkyl, by one or more Ra-1Substituted C1～C6An alkyl group; when R isa-1Independently a plurality thereof, the same or different;
R24independently is
Figure FDA0003230989820000013
n1 and n2 are independently 0, 1,2, 3 or 4; n3 is 0, 1,2 or 3;
R1-1、R2-1、R1-2、R2-2、R1-3、R1-4、R2-3independently hydrogen, deuterium, halogen, cyano, C1～C6Alkyl, by one or more Rb-1Substituted C1～C6Alkyl radical, C6～C10Aryl radicals, substituted by one or more Rb-3Substituted C6～C10Aryl, pyridyl, substituted by one or more Rb-4Substituted pyridyl or
Figure FDA0003230989820000014
When R isb-1、Rb-3And Rb-4When there are plural, Rb-1、Rb-3And Rb-4Independently are the same or different; wherein the content of the first and second substances,
Figure FDA0003230989820000015
is composed of
Figure FDA0003230989820000016
And
Figure FDA0003230989820000017
connected by a single bond;
Figure FDA0003230989820000018
independently of the others, phenyl, substituted by one or more Rc-1Substituted phenyl, pyridyl, or substituted with one or more Rc-2A substituted pyridyl group; when R isc-1And Rc-2Independently a plurality thereof, the same or different;
Ra-1、Rb-1、Rb-3、Rb-4、Rc-1、Rc-2and Rd-1Independently the following substituents: deuterium, halogen, cyano, trifluoromethyl or C1～C6An alkyl group.
2. The 1,3, 5-triazines of formula I as claimed in claim 1, wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently halogen, said halogen is independently fluorine, chlorine, bromine or iodine;
and/or, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently halogen, said halogen is independently fluorine, chlorine, bromine or iodine;
and/or when
Figure FDA0003230989820000021
When the aryl is a phenyl group independently, the phenyl group,
Figure FDA0003230989820000022
independently is
Figure FDA0003230989820000023
And/or the presence of a gas in the gas,
Figure FDA0003230989820000024
same as R21、R22And R23The same;
and/or, when L is
Figure FDA0003230989820000025
When R is24Independently located at
Figure FDA0003230989820000026
And
Figure FDA0003230989820000027
ortho, meta or para to the attachment site;
and/or, Ra-1、Rb-1、Rb-3、Rb-4、Rc-1、Rc-2And Rd-1Independently halogen, said halogen is independently fluorine, chlorine, bromine or iodine;
and/or, Ra-1、Rb-1、Rb-3、Rb-4、Rc-1、Rc-2And Rd-1Independently is C1～C6In the alkyl group, said C1～C6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl;
and/or, Ra-1、Rb-1、Rb-3、Rb-4、Rc-1、Rc-2And Rd-1Independently of the number of (a) is 1,2 or 3;
and/or, R24Independently is
Figure FDA0003230989820000028
3. The 1,3, 5-triazines of formula I as claimed in claim 2, wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently hydrogen or halogen;
and/or, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently halogen, said halogen is independently fluorine;
and/or, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently halogen, said halogen is independently fluorine;
and/or, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently is C1～C6Alkyl, by one or more Ra-1Substituted C1～C6Alkyl radicalIn (b), the C1～C6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl;
and/or, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently is C1～C6Alkyl, by one or more Rb-1Substituted C1～C6In the alkyl group, said C1～C6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl;
and/or, R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently is C6～C10Aryl radicals or by one or more Rb-3Substituted C6～C10In aryl, said C6～C10Aryl is independently phenyl or naphthyl;
and/or when
Figure FDA0003230989820000029
When the aryl is a phenyl group independently, the phenyl group,
Figure FDA00032309898200000210
independently is
Figure FDA00032309898200000211
Figure FDA00032309898200000212
And/or when R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And R23Independently by one or more Ra-1Substituted C1～C6When alkyl, said substituted C1～C6Alkyl is independently trifluoromethyl;
and/or when R1-1、R2-1、R1-2、R2-2、R1-3、R1-4And R2-3Independently by one or more Rb-1Substituted C1～C6When alkyl, said substituted C1～C6Alkyl is independently trifluoromethyl.
4. The 1,3, 5-triazines of formula I as claimed in claim 3, wherein,
Figure FDA0003230989820000031
independently is
Figure FDA0003230989820000032
Figure FDA0003230989820000033
And/or the presence of a gas in the gas,
Figure FDA0003230989820000034
independently is
Figure FDA0003230989820000035
Figure FDA0003230989820000036
And/or the presence of a gas in the gas,
Figure FDA0003230989820000041
independently is
Figure FDA0003230989820000042
5. The 1,3, 5-triazines of formula I as claimed in claim 4, wherein,
Figure FDA0003230989820000043
independently is
Figure FDA0003230989820000044
Figure FDA0003230989820000045
And/or the presence of a gas in the gas,
Figure FDA0003230989820000046
independently is
Figure FDA0003230989820000047
Figure FDA0003230989820000051
6. The 1,3, 5-triazine compound of formula I as claimed in claim 1, which is any one of the following compounds:
Figure FDA0003230989820000052
Figure FDA0003230989820000061
Figure FDA0003230989820000071
Figure FDA0003230989820000081
7. use of a 1,3, 5-triazine compound of formula I according to any one of claims 1 to 6 as an electronic material.
8. Use according to claim 7, wherein the electronic material is an electron transport material and/or an electron acceptor material.
9. The application of the 1,3, 5-triazine compound shown in the formula I as claimed in any one of claims 1 to 6 in the field of organic electroluminescent devices.
10. The use according to claim 9, wherein the 1,3, 5-triazine compound shown in formula I is used for preparing one or more of an electron transport layer, a hole blocking layer and a light emitting layer in an organic electroluminescent device.
11. An organic electroluminescent composition, which comprises an electron donor material and the 1,3, 5-triazine compound shown in the formula I as claimed in any one of claims 1 to 6.
12. The organic electroluminescent composition of claim 11, wherein the electron donor material is a phenyl or naphthyl carbazole electron donor material;
and/or the molar ratio of the 1,3, 5-triazine compound shown in the formula I to the electron donor material is 3:1 to 1: 3;
and/or, the organic electroluminescent composition also comprises a doped luminescent material.
13. The organic electroluminescent composition according to claim 12, wherein the electron donor material is a phenyl or naphthyl carbazole electron donor material, and the phenyl or naphthyl carbazole electron donor material has a structure containing 2 to 3 phenyl carbazoles or naphthyl carbazolyl carbazoles;
and/or the molar ratio of the 1,3, 5-triazine compound shown in the formula I to the electron donor material is 1: 1;
and/or when the organic electroluminescent composition further comprises a doped luminescent material, the doped luminescent material is a fluorescent luminescent material and/or a phosphorescent luminescent material.
14. The organic electroluminescent composition of claim 13, wherein the electron donor material is any one of the following compounds:
Figure FDA0003230989820000082
Figure FDA0003230989820000091
and/or, the organic electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a fluorescent luminescent material, the mass percentage of the doped luminescent material in the composition is 0.5WT％-2.0WT％；
And/or, the organic electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a phosphorescent luminescent material, the mass percentage of the doped luminescent material in the composition is 5.0WT％-15.0WT％；
And/or, the organic electroluminescent composition further comprises a doped luminescent material, and when the doped luminescent material is a phosphorescent luminescent material, the doped luminescent material is any one of the following compounds:
Figure FDA0003230989820000101
Figure FDA0003230989820000102
wherein, Ra1、Ra3、Rb1、Rb3、Rd1、Rd3、Re4、Re5、Re6、Rf7、Rf8、Rf9、Rb10-1、Rb10-2、Re10-1、Re10-2、Rf10-1And Rf10-2Independently H or a linear or branched alkyl group containing 1-5C; ra2、Rb2And Rd2Independently H, straight or branched chain alkyl containing 1-5C, phenyl or phenyl substituted by straight or branched chain alkyl containing 1-5C;
Figure FDA0003230989820000103
independently a six-membered aromatic heterocyclic ring containing 1-2N;
and/or, the organic electroluminescent composition further comprises a doped luminescent material, and when the doped luminescent material is a fluorescent luminescent material, the doped luminescent material is any one of the following compounds:
Figure FDA0003230989820000104
Figure FDA0003230989820000111
Figure FDA0003230989820000112
wherein Rg11-1、Rg11-2、Rh11-1、Rh11-2Independently a straight or branched chain alkyl group containing 1 to 5 carbons; rg (Rg)12-1、Rg12-2、Rh13-1、Rh13-2、Rh13-3And Rh13-4Represents a linear or branched alkyl group containing 1 to 5C, F or CF3；Ri14-1、Ri14-2、Ri15-1、Ri15-2、Rj16-1、Rj16-2、Rj17-1、Rj17-2、Rk18-1、Rk18-2、Rk18-3、Rk18-4、Rk19-1、Rk19-2、Rk19-3、Rk19-4、Rl20-1、Rl20-2、Rl20-3、Rl20-4、Rm23-1、Rm24-1、Rn26-1、Rn27-1、Ro29-1、Ro30-1、Ro32-1、Rp34-1、Rp35-1、Rp36-1And Rp37-1Independently a linear or branched alkyl group containing 1 to 5C, cyclohexane or cumene; rm22-1、Rn25-1、Ro28-11And Rp33-1Is a straight chain or branched chain alkyl containing 1-4C.
15. The organic electroluminescent composition of claim 14, wherein the electron donor material is
Figure FDA0003230989820000113
And/or, the organic electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a fluorescent luminescent material, the mass percentage of the doped luminescent material in the composition is 1.0WT％；
And/or, the organic electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a phosphorescent luminescent material, the mass percentage of the doped luminescent material in the composition is 10.0WT％；
And/or, the organic electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a phosphorescent luminescent material, the doped luminescent material is
Figure FDA0003230989820000121
And/or, said organicThe electroluminescent composition also comprises a doped luminescent material, and when the doped luminescent material is a fluorescent luminescent material, the doped luminescent material is
Figure FDA0003230989820000122
16. Use of an organic electroluminescent composition as claimed in any one of claims 11 to 15 as an organic electroluminescent material.
17. An organic electroluminescent element comprising the organic electroluminescent composition according to any one of claims 11 to 15.
18. The organic electroluminescent device of claim 17, wherein the organic electroluminescent composition is a light-emitting layer;
and/or the organic electroluminescent device also comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises the light-emitting layer and also comprises any one or combination of a plurality of hole injection layers, hole transport layers, electron blocking layers, hole blocking layers, electron transport layers and electron injection layers.
19. The organic electroluminescent device according to claim 17, wherein when the organic luminescent functional layer comprises an electron transport layer, the electron transport material in the electron transport layer has the same structure as the 1,3, 5-triazine compound in the organic electroluminescent composition.
20. An organic electroluminescent device as claimed in any one of claims 17 to 19 for use in the preparation of an organic electroluminescent display or an organic electroluminescent lighting source.
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