CN111205237B - Triamine derivative and organic electroluminescent device thereof - Google Patents

Triamine derivative and organic electroluminescent device thereof Download PDF

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CN111205237B
CN111205237B CN202010032751.7A CN202010032751A CN111205237B CN 111205237 B CN111205237 B CN 111205237B CN 202010032751 A CN202010032751 A CN 202010032751A CN 111205237 B CN111205237 B CN 111205237B
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孙敬
朱鸫达
鲁秋
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention discloses a triamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The invention aims to solve the technical problems that the current hole transport material can not effectively block electrons, the light extraction material can not effectively couple out the light trapped in the device, and the organic electroluminescent device has low luminous efficiency. The triamine derivatives of the present invention contain at least one benzoxazolyl or benzothiazolyl group. The organic electroluminescent device comprises an anode, a luminescent layer, a cathode and a hole transport layer or a light extraction layer, wherein the hole transport layer or the light extraction layer contains the triamine derivative. The triamine derivative can be used as a hole transport material and a light extraction material, and can effectively improve the luminous efficiency of the device when being applied to an organic electroluminescent device.

Description

Triamine derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a triamine derivative and an organic electroluminescent device thereof.
Background
An Organic Light-Emitting Diode (OLED) is also called an Organic Light-Emitting Device (OLED). The organic electroluminescent device is a device which takes an organic material as an active luminescent layer under the action of an electric field. Since Duncuon and VanSlyke successfully prepare the first low-voltage driven organic electroluminescent device by adopting an organic small molecular film for the first time in 1987, OLEDs (organic light emitting diodes) are widely concerned and rapidly developed, and have good industrialization prospects in the aspects of panel display and solid-state illumination mainly according to inherent characteristics and advantages. Compared with the conventional Liquid Crystal Display (LCD), the OLED has many advantages such as wide viewing angle, fast response, low power consumption, high contrast, flexibility, ultra-thin and ultra-light, and is a very ideal new-generation flat panel display technology. OLED products such as televisions, cell phones, notebook computers, smart watches, and virtual/augmented reality (VR/AR) have been successively introduced by many domestic and foreign companies.
Organic electroluminescent devices are typically classic sandwich structures consisting of a cathode, an anode and organic functional layers, wherein the organic functional layers mainly comprise: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In addition, a light extraction layer (CPL) is usually introduced outside the cathode in top-emitting devices. When a device is biased with a dc voltage, holes are injected from the anode and transferred to the light-emitting layer via the Highest Occupied Molecular Orbital (HOMO), and electrons are injected from the cathode and transferred to the light-emitting layer via the Lowest Unoccupied Molecular Orbital (LUMO). The electrons and holes combine in the light-emitting layer to produce excitons, which, when they release energy in the form of light radiation, are the electroluminescence of the light-emitting device.
Each organic functional layer in the organic electroluminescent device plays a role and plays a different role in the device, wherein the hole transport layer has a basic role in improving the transport efficiency of holes in the device. A potential barrier is generated between the hole transport layer and the anode from the viewpoint of ionization energy, and the potential barrier is one of factors affecting the stability of the device, and the smaller the potential barrier is, the higher the stability of the device is. In addition, the hole transport material must have an energy and structure compatible with the emissive layer. The good hole transport material has the advantages of good electrochemical stability, good film forming property, high hole mobility and the like.
In addition, the light extraction layer in the top emission device is used for coupling out the light trapped in the device, so that the luminous efficiency of the device is improved. Through recent research, the loss of the external optical coupling efficiency of the top-emitting device is mainly caused by surface plasmon resonance loss and waveguide modes due to the existence of the metal cathode. A light extraction layer is added outside the metal cathode, and the wave vector of free light is improved by the layer, so that energy limited in the device can be coupled out in the form of light, and the effect of enhancing the light extraction efficiency is achieved.
However, most of the currently used hole transport materials do not have a function of blocking electrons, resulting in a decrease in the light emission efficiency of the device. In addition, the research on light extraction materials at home and abroad is less, and the performance of most light extraction materials is poorer, so that the light trapped in the device can not be effectively coupled out. Moreover, most functional materials have a single function, and even if an individual material has two or more functions, the performance is not good.
Disclosure of Invention
The invention provides a triamine derivative and an organic electroluminescent device thereof, aiming at solving the problems that the existing hole transport material can not effectively block electrons, a light extraction material can not effectively couple out light trapped in the device and the organic electroluminescent device has low luminous efficiency. Among them, the triamine derivative of the present invention can be used for both the hole transport layer and the light extraction layer.
The present invention has been accomplished by the above-mentioned objects, which can be achieved by using a triamine derivative represented by the following formula I as a hole transport material or a light extraction material of an organic electroluminescent device.
The invention provides a triamine derivative, which is shown as a formula I,
Figure BDA0002364918130000021
wherein, Ar and Ar are1、Ar2、Ar3、Ar4Independently selected from one of the groups shown in the following,
Figure BDA0002364918130000022
and, Ar1、Ar2At least one of which is selected from one of the groups shown below,
Figure BDA0002364918130000023
x is selected from O or S; the L is selected from one of single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30; the R is selected from one of hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; the R is0One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
The invention also provides an organic electroluminescent device, which comprises an anode, a luminescent layer and a cathode, wherein the luminescent layer is positioned between the anode and the cathode, the organic electroluminescent device also comprises at least one of a hole transport layer and a light extraction layer, the hole transport layer is positioned between the anode and the luminescent layer, the light extraction layer is positioned on one side of the cathode far away from the anode, and the hole transport layer or the light extraction layer comprises the triamine derivative.
Has the advantages that: the triamine derivative provided by the invention has two functions as an organic functional material, the triamine derivative can be used as a hole transport material firstly, the triamine derivative can be used as a hole transport material, the hole transport material can transport holes and can also effectively block electrons, the electrons are trapped in a light-emitting layer, so that the holes and the electrons can be effectively combined in the light-emitting layer to form excitons, the higher the recombination probability of the electrons and the holes is, the more the number of the formed excitons in unit time is, the more the energy is emitted, and correspondingly, the higher the light-emitting efficiency of the device is. Secondly, the triamine derivative provided by the invention can also be used as a light extraction material of a top emission device, and the triamine derivative can be used as the light extraction material to effectively couple out light trapped in the device, so that the luminous efficiency of the device is improved.
Drawings
FIG. 1 is a drawing showing Compound 1 of the present invention1H NMR chart;
FIG. 2 is a drawing showing Compound 11 of the present invention1H NMR chart;
FIG. 3 is a drawing showing a preparation of compound 37 of the present invention1H NMR chart;
FIG. 4 is a drawing of Compound 39 of the present invention1H NMR chart;
FIG. 5 is a drawing showing a preparation of compound 78 of the present invention1H NMR chart;
FIG. 6 is a drawing showing a scheme for preparing a compound 79 of the present invention1H NMR chart;
FIG. 7 is a drawing showing a scheme for preparing a compound 142 of the present invention1H NMR chart.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.
The term "unsubstituted" in the "substituted or unsubstituted" as used herein means that hydrogen in a group is not replaced by another substituent. The term "substituted" in the "substituted or unsubstituted" as used herein means that hydrogen in a group is replaced by another substituent, the hydrogen replaced by the substituent may be one or more, and when a plurality of hydrogens are replaced by substituents, the substituents may be the same or different. The substituent group is selected from one or more of the following: deuterium, a halogen atom, cyano; C1-C15 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, mesityl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like; the aryl group having C6 to C30 includes, but is not limited to,
Figure BDA0002364918130000031
Figure BDA0002364918130000041
the heteroaryl group having C3-C30 includes, but is not limited to,
Figure BDA0002364918130000042
the "C6 to C30" in the "substituted or unsubstituted aryl group having C6 to C30" in the present invention means the number of carbon atoms contained in the unsubstituted aryl group, and the number of carbon atoms of the substituent is not included; "C3 to C30" in "substituted or unsubstituted heteroaryl group of C3 to C30" means the number of carbon atoms contained in the unsubstituted heteroaryl group, and the number of carbon atoms of the substituent is not included; "C1 to C15" in the "substituted or unsubstituted alkyl group having C1 to C15" means the number of carbon atoms contained in the unsubstituted alkyl group, and the number of carbon atoms of the substituent is not included. And so on.
The chain alkyl group having three or more carbon atoms described in the present invention includes isomers thereof, and for example, propyl groups include n-propyl groups and isopropyl groups; butyl includes n-butyl, sec-butyl, isobutyl and tert-butyl. And so on.
The alkyl refers to a hydrocarbon group formed by subtracting one hydrogen atom from alkane molecules, and can be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc., but is not limited thereto; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, etc.; the cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like, but is not limited thereto.
The aryl group refers to a general term of monovalent groups left after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and can be monocyclic aryl, polycyclic aryl or fused ring aryl. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group having two or more aromatic rings in a molecule and fused together by sharing two adjacent carbon atoms, and includes, but is not limited to, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, pyrenyl, triphenylene, spirobifluorenyl, and the like.
The heteroaryl group in the invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group by heteroatoms, wherein the heteroatoms include but are not limited to oxygen, sulfur, nitrogen, silicon, boron or phosphorus atoms, the connecting site of the heteroaryl group can be positioned on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group can be a monocyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl and the like, but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, benzofuranyl, dibenzofuranyl, benzodibenzofuranyl, benzothienyl, dibenzothiophenyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, xanthyl, thianthrenyl, azaanthracyl and the like.
The arylene group in the present invention refers to a general term of monovalent group remaining after two hydrogen atoms are removed from the aromatic nucleus carbon of a substituted or unsubstituted aromatic compound molecule, and may be monocyclic arylene group, polycyclic arylene group or fused ring arylene group. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the fused ring arylene group includes naphthylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, and the like, but is not limited thereto.
Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic nuclear carbons in the arylene group is replaced with a heteroatom, including but not limited to oxygen, sulfur, nitrogen, silicon, boron, or phosphorus, which may be a monocyclic heteroarylene, a polycyclic heteroarylene, or a fused ring heteroarylene. The monocyclic heteroarylene group includes a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes, but is not limited to, a bipyridyl group and the like; the fused ring heteroarylene group includes a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, an acridinylene group and the like, but is not limited thereto.
The invention provides a triamine derivative, which is shown as a formula I,
Figure BDA0002364918130000051
wherein, Ar and Ar are1、Ar2、Ar3、Ar4Independently selected from one of the groups shown in the following,
Figure BDA0002364918130000052
and, Ar1、Ar2At least one of which is selected from one of the groups shown below,
Figure BDA0002364918130000053
x is selected from O or S; the L is selected from one of single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30; the R is selected from one of hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; the R is0One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
Preferably, Ar is selected from one of the groups shown as follows,
Figure BDA0002364918130000061
the L is selected from one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted furylene and substituted or unsubstituted thienylene;
r is selected from one of hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted furyl and substituted or unsubstituted thienyl;
the R is0One selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl.
Preferably, Ar is selected from one of the groups shown as follows,
Figure BDA0002364918130000062
Figure BDA0002364918130000071
preferably, the triamine derivative is selected from one of formulas I-1 to I-5 shown in the specification,
Figure BDA0002364918130000072
wherein Ar is selected from one of the groups shown in the specification,
Figure BDA0002364918130000073
Figure BDA0002364918130000081
preferably, Ar is3、Ar4Independently selected from one of the groups shown in the following,
Figure BDA0002364918130000082
preferably, Ar is3、Ar4Independently selected from one of the groups shown in the following,
Figure BDA0002364918130000083
further, the triamine derivative is selected from one of the structures shown in the following,
Figure BDA0002364918130000084
Figure BDA0002364918130000091
Figure BDA0002364918130000101
Figure BDA0002364918130000111
Figure BDA0002364918130000121
Figure BDA0002364918130000131
Figure BDA0002364918130000141
Figure BDA0002364918130000151
Figure BDA0002364918130000161
some specific chemical structures of the triamine derivative shown in the formula I according to the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all that is based on the structure shown in the formula I, the substituent groups are the groups defined above, should be included.
The invention also provides an organic electroluminescent device, which comprises an anode, a luminescent layer and a cathode, wherein the luminescent layer is positioned between the anode and the cathode, the organic electroluminescent device also comprises at least one of a hole transport layer and a light extraction layer, the hole transport layer is positioned between the anode and the luminescent layer, the light extraction layer is positioned on one side of the cathode far away from the anode, and the hole transport layer or the light extraction layer comprises the triamine derivative.
Further, the light-emitting layer further comprises a hole transport layer, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the second hole transport layer comprises the triamine derivative provided by the invention.
Further, the present invention also includes a light extraction layer containing the triamine derivative of the present invention.
The organic electroluminescent device of the present invention may further include any one or any multiple of a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, an exciton blocking layer, and a charge generation layer.
The film thickness of each layer is not particularly limited, and may be selected so as to obtain good device performance. Generally, if the film thickness is too thick, the performance of the organic electroluminescent device may be degraded, for example, the driving voltage is high, and the light emitting efficiency is low. If the film thickness is too thin, defects such as pinholes may occur, and a desired light emission luminance may not be obtained. Therefore, the film thickness is usually 5nm to 10 μm, preferably 10nm to 0.2. mu.m.
In particular, the film thickness of the hole transport layer is not particularly limited, but is preferably 5nm to 300 nm. In addition, when the hole transport layer has a two-layer structure, the film thickness of each layer is not particularly limited, and the film thickness of the first hole transport layer is preferably 10nm to 300nm, more preferably 30nm to 250nm, and most preferably 50nm to 150 nm; the film thickness of the second hole transport layer is preferably 5nm to 100nm, more preferably 5nm to 50nm, and most preferably 5nm to 30 nm.
In particular, the thickness of the light extraction layer is not particularly limited, but is preferably 10nm to 150nm, more preferably 30nm to 100nm, and most preferably 40nm to 80 nm.
The film thickness of the anode or the cathode varies depending on the material, and is usually 10nm to 1 μm, preferably 10nm to 200 nm.
The organic electroluminescent device of the present invention can be manufactured by a known method using a known material, however, the structure of the organic electroluminescent device is not limited thereto.
The substrate comprises a glass plate, a quartz plate or a flexible substrate and the like, wherein the flexible substrate comprises polyethylene naphthalate (PEN), polyethylene terephthalate (PET), poly tert-butyl acrylate (PtBA), polyether sulfone resin (PES), metal foil, ultrathin glass, a paper substrate and the like.
The anode material has the characteristics of high conductivity, high work function and the like, so that holes can be effectively injected into an organic matter layer. Selected from one or more of the materials, conductive oxides, metals, etc., but not limited thereto. The conductive Oxide includes Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Aluminum Zinc Oxide (AZO), Indium Oxide (InO), zinc Oxide (ZnO), zinc aluminum Oxide (Al: ZnO), and the like. The metal includes silver (Ag), gold (Au), aluminum (Al), copper (Cu), nickel (Ni), molybdenum (Mo), titanium (Ti), zinc (Zn), palladium (Pd), platinum (Pt), and the like. The anode of the invention can be a single-layer structure or a multi-layer structure with more than two layers, and the anode material contained in each layer can be a single material or a mixed material.
The cathode material has the characteristics of low work function and the like, so that electrons can be effectively injected into an organic layer. It is selected from one or more of the following materials, metals, metal alloys, etc., but is not limited thereto. The metals include alkali metals, alkaline earth metals, lanthanide metals, and the like. The metal alloy includes magnesium-silver alloy (Mg: Al), lithium-aluminum alloy (Li: Al), lithium-calcium-magnesium alloy (Li: Ca: Mg) and the like. The cathode of the invention can be a single-layer structure or a multi-layer structure with more than two layers, and the cathode material contained in each layer can be a single material or a mixed material.
The hole injection layer of the invention has the functions of increasing hole injection between the hole transport layer and the anode interface and improving the efficiency and the service life of the device. The hole injection material of the present invention is selected from one or more of metal oxides, phthalocyanine-based compounds, arylamine-based compounds, cyano group-containing conjugated materials, polymers, and the like, but is not limited thereto. The metal oxide comprises molybdenum trioxide (MoO)3) Silver oxide (AgO), vanadium pentoxide (V)2O5) Tungsten trioxide (WO)3) Nickel oxide (NiO), titanium dioxide (TiO)2) And the like. The phthalocyanine compounds comprise copper (II) phthalocyanine (CuPc), oxytitanium phthalocyanine (TiOPC), zinc phthalocyanine (ZnPc) and the like. The arylamine compound comprises 4,4' -tri [ 2-naphthyl phenylamino group]Triphenylamine (2T-NATA), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), and the like. The cyano-containing conjugated material is 7,7,8, 8-Tetracyanoterephthalquinodimethane (TCNQ), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ) and the like. The high polymer material comprises poly (N-vinyl carbazole) (PVK), poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (PEDOT/PSS) and the like. The hole injection layer of the present invention may have a single-layer structure or two or more layersIn the multilayer structure, the hole injection material contained in each layer may be a single material or a mixed material.
The hole transport layer has the effects of improving the balance of injection and transport of the device hole, and improving the efficiency and the service life of the device. The hole transport material is selected from one or more of the following materials, aromatic amine compounds, carbazole derivatives, and the like, but is not limited thereto. The aromatic amine compound includes N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (Spiro-TAD), and the like. The carbazole derivative includes 1,3, 5-tri (9-carbazolyl) benzene (TCB), 4' -tri (carbazol-9-yl) triphenylamine (TCTA), and the like. The hole transport layer of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the hole transport material contained in each layer may be a single material or a mixed material. Preferred are the triamine derivatives of the formula I according to the invention.
The light emitting layer of the present invention refers to an organic layer capable of emitting photons. The light-emitting layer of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the light-emitting material contained in each layer may be a single material or a mixed material. The light emitting material is classified into a blue light emitting material, a green light emitting material, and a red light emitting material.
The blue light emitting material is selected from one or more of anthracene derivatives, fluorene derivatives, perylene derivatives, styrylamine derivatives, metal complexes, and the like, but is not limited thereto. Specifically, 9, 10-bis- (2-naphthyl) Anthracene (ADN), 9- [4- (2- (7- (N, N-diphenylamino) -9, 9-diethylfluoren-2-yl) vinyl) phenyl ] -9-phenyl-fluorene (DPAFVF), 9-bis (3- (9-phenyl-carbazolyl)) -2, 7-dipyrenylfluorene (DCDPF), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (di-p-tolylamino) styryl ] biphenyl (DPAVBi), bis (4, 6-difluorophenylpyridine-C2, N) iridium picolinate (FIrpic), and the like.
The green luminescent material is selected from one or more of the following materialsThere are various coumarin dyes, quinacridone copper derivatives, polycyclic aromatic hydrocarbons, diamine anthracene derivatives, carbazole derivatives, metal complexes, etc., but are not limited thereto. Specifically, coumarin 6(C-6), coumarin 545T (C-525T), quinacridone copper (QA), N '-Dimethylquinacridone (DMQA), 5, 12-Diphenylnaphthonaphthalene (DPT), N10, N10' -diphenyl-N10, N10 '-bisanthracene-9, 9' -dianthracene-10, 10 '-diamine (BA-NPB), 9' - (5- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) benzene-1, 2, 3-triyl) tris (3, 6-dimethyl-9H-carbazole) (TmCzTrz), tris (8-hydroxyquinoline) aluminum (III) (Alq)3) Tris (2-phenylpyridine) iridium (Ir (ppy)3) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)2(acac)) and the like.
The red light emitting material is selected from one or more of materials described below, DCM series materials, metal complexes, and the like, but is not limited thereto. Specifically, 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), 2- [ 2-methyl-6- [2- (2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H-benzo [ ij)]Quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene]Malononitrile (DCJT), bis (1-phenylisoquinoline) (acetylacetone) iridium (III) (Ir (piq))2(acac)), platinum octaethylporphyrin (PtOEP), bis (2- (2 '-benzothienyl) pyridine-N, C3') (acetylacetone) iridium (Ir (btp)2(acac) and the like.
When the above-mentioned light-emitting material is used as a guest material, it is necessary to select a suitable host material to match it, and the host material is preferably a material having a higher lowest unoccupied orbital level and a lower highest occupied orbital level than the guest material. The host material includes a metal complex, a fluorene derivative, an anthracene derivative, a carbazole derivative, and the like, but is not limited thereto. Specifically, tris (8-hydroxyquinoline) aluminum (III) (Alq)3) 2, 7-bis [9, 9-bis (4-methylphenyl) -fluoren-2-yl]-9, 9-bis (4-methylphenyl) fluorene (TDAF), 9, 10-bis (2-naphthyl) Anthracene (ADN), 1,3, 5-tris (9-carbazolyl) benzene (TCP), 4 '-bis (9-Carbazole) Biphenyl (CBP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), and the like.
The hole blocking layer of the present invention has a function of blocking the migration of holes to the electron transport layer. The hole blocking material is selected from one or more of phenanthroline derivatives, aluminum complexes, benzimidazole derivatives, and the like, but is not limited thereto. The phenanthroline derivative includes 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-di (naphthalene-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), and the like. The aluminum complex includes bis (8-hydroxy-2-methylquinoline) - (4-phenylphenoxy) aluminum (BAlq) and the like. The benzimidazole derivative includes 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi) and the like. The hole blocking layer of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the hole blocking material contained in each layer may be a single material or a mixed material.
The electron transport layer of the present invention has the function of injecting electrons and balancing carriers. The electron transport material is selected from one or more of metal complexes, oxazole derivatives, imidazole derivatives, phenanthroline derivatives, pyridine derivatives, and the like, but is not limited thereto. The metal complex comprises tris (8-hydroxyquinoline) aluminum (III) (Alq)3) Bis (2-methyl-8-quinolinolato) (4-phenylphenol) aluminum (III) (BALq), and the like. The oxazole derivative is selected from 2, 5-di- (4-naphthyl) -1,3, 4-oxadiazole (BND for short), 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD) and the like. The imidazole derivative is selected from 1,3, 5-tri (N-phenyl-2-benzimidazole) benzene (TPBi) and the like. The phenanthroline derivatives include 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 2, 9-di (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen), and the like. The pyridine derivatives include 3,3'- [5' - [3- (3-pyridyl) phenyl](TmPyPB) and the like. The electron transport layer of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the electron transport material contained in each layer may be a single material or a mixed material.
The electron injection layer has the functions of reducing the potential barrier between the electron transport layer and the cathode interface, improving the electron injection efficiency and prolonging the service life of the device. The electron injecting material is selected from one or more of materials described below, alkali metal compounds, alkali metal fluorides, and the like, but is not limited thereto. The alkali metal compound comprises lithium oxide(LiO) and lithium boron oxide (LiBO)2) Silicon potassium oxide (K)2SiO3) Cesium carbonate (Cs)2CO3) And the like. The fluoride includes lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF), and the like. The electron injection layer of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the electron injection material contained in each layer may be a single material or a mixed material.
The light extraction layer according to the present invention is preferably a triamine derivative according to the present invention. The light extraction material of the present invention may have a single-layer structure or a multilayer structure having two or more layers, and the light extraction material contained in each layer may be a single material or a mixed material.
The method for forming each layer of the organic electroluminescent element of the present invention is not particularly limited, and known methods such as a dry film forming method and a wet film forming method can be used. The dry film formation method includes a vacuum deposition method, a sputtering method, a plasma method, and the like. The wet film formation method includes, but is not limited to, spin coating, dipping, ink jet, and the like.
The organic electroluminescent device can be widely applied to the fields of flat panel display, solid illumination, organic photoreceptors or organic thin film transistors and the like.
The synthetic route of the triamine derivatives of formula I of the present invention is not particularly limited, and the triamine derivatives of the present invention can be prepared by using conventional reactions well known to those skilled in the art. For example, a carbon-carbon coupling reaction such as Ullmann reaction, Buchwald-Hartwig reaction, and the like, or a carbon-carbon coupling reaction such as Suzuki reaction (Suzuki).
For example, the compounds of formula I of the present invention can be obtained by the following synthetic route:
Figure BDA0002364918130000201
the starting materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
Preparation of the Compounds
Description of raw materials and reagents: the raw materials and reagents used in the invention are all pure reagents.
Description of the characterizing device: mass Spectrometry an AXIMA-CFR plus matrix-assisted laser desorption ionization flight Mass spectrometer from Kratos Analytical, Inc. of Shimadzu corporation, U.S.A., was used, with chloroform as the solvent. The elemental analysis was carried out by using a Vario EL cube type organic element analyzer of Elementar, Germany, and the sample mass was 5 to 10 mg. Nuclear magnetic resonance (1HNMR) Using a Bruker-510 type nuclear magnetic resonance spectrometer (Bruker, Germany), 600MHz, CDCl3As solvent, TMS as internal standard.
Synthesis example 1: preparation of Compound 1
Figure BDA0002364918130000202
(1) Sodium tert-butoxide (28.8g,0.30mol), bis (4-bromophenyl) amine (32.7g,0.10mol), 2- (4-bromophenyl) benzoxazole (27.4g,0.10mol), tris (dibenzylideneacetone) dipalladium (91.5mg,0.10mmol) and toluene (250mL) were added to a 500mL reaction flask under nitrogen protection, and stirred for 30 minutes, followed by addition of tri-tert-butylphosphine (0.10mL of a 1.0M solution in toluene, 0.10mmol) and reaction under reflux conditions for 13 hours. Pouring the reaction solution into a 1.5L beaker, adding toluene (200ml) and water (400ml), stirring for 10 minutes, carrying out suction filtration, leaching a filter cake with water until the filtrate is neutral, leaching with toluene and ethanol respectively, draining, and recrystallizing with ethanol to obtain a solid intermediate A-1(42.1g, yield of 81%), and solid purity being not less than 99.9% by HPLC (high performance liquid chromatography).
(2) To a 1.25L reaction flask were added 4- (2-benzoxazolyl) aniline (47.3g,0.225mol), bromobenzene (23.7mL,0.225mol), sodium tert-butoxide (28.8g,0.30mol), palladium acetate (2.06g,2.25mmol), tri-tert-butylphosphine (9.0mL of a 1.0M solution in toluene, 9.0mmol) and toluene (500mL) under nitrogen. The reaction was carried out under reflux for 2 hours. After the reaction is finished, cooling to room temperature, filtering the reaction solution by using kieselguhr, concentrating the filtrate, and recrystallizing by using methanol to obtain the intermediate B-1(58.0g, the yield is about 90%), wherein the solid purity is not less than 99.9% by HPLC (high performance liquid chromatography).
(3) To a 1000mL reaction flask, toluene (500mL), sodium tert-butoxide (28.8g,0.30mol), intermediate A-1(31.2g,0.06mol), intermediate B-1(34.4g,0.12mol), tris (dibenzylideneacetone) dipalladium (1.10g,1.2mmol), and tri-tert-butylphosphine (1.2mL of a 1.0M solution in toluene, 1.2mmol) were added under argon protection, and reacted for 3 hours under reflux. Cooling the reaction solution to room temperature, extracting with dichloromethane, washing the organic phase with saturated sodium chloride aqueous solution, washing with water, drying with anhydrous magnesium sulfate, spinning out the organic solvent, and recrystallizing with toluene to obtain solid compound 1(43.0g, yield 77%), wherein the solid purity is not less than 99.9% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 930.29 (calculated value: 931.07). Theoretical element content (%) C63H42N6O3: c, 81.27; h, 4.55; n, 9.03; o, 5.16; measured elemental content (%): c, 81.49; h, 4.62; n, 9.31; and O, 5.23.1H NMR(600MHz,CDCl3And, ppm): 8.12(d,2H),8.10(d,4H),7.76 to 7.71(m,3H),7.58 to 7.51(m,3H),7.39 to 7.34(m,4H),7.33 to 7.31(m,5H),7.24 to 7.22(m,4H),7.20(d,2H),7.19 to 7.13(m,15H). The above results confirm that the product is obtained as the objective product.
Synthesis example 2: preparation of Compound 6
Figure BDA0002364918130000211
The bromobenzene in synthesis example 1- (2) was replaced by equimolar 9, 9-dimethyl-2-bromofluorene, and the other steps were carried out in the same manner to obtain compound 6(52.4g, yield about 75%) with a solid purity ≧ 99.9% by HPLC. Mass spectrum m/z: 1162.23 (calculated value: 1163.39). Theoretical element content (%) C81H58N6O3: c, 83.63; h, 5.03; n, 7.22; o, 4.13; measured elemental content (%): c, 83.12; h, 5.11; n, 7.14; and O, 4.25. The above results confirmed that the obtained product was the objective product.
Synthesis example 3: preparation of Compound 11
Figure BDA0002364918130000221
2- (4-bromophenyl) benzoxazole in Synthesis example 1- (1) was replaced with equimolar 3-bromodibenzo [ B, D]Furan, the same procedures were repeated to give compound 11(35.3g, yield about 65%) with a solid purity of 99.9% by HPLC. Mass spectrum m/z: 903.36 (calculated value: 904.04). Theoretical element content (%) C62H41N5O3: c, 82.37; h, 4.57; n, 7.75; o, 5.31; measured elemental content (%): c, 82.47; h, 4.63; n, 7.69; and O, 5.54.1H NMR(600MHz,CDCl3And, ppm): 8.03(dd,1H), 7.85-7.80 (m,4H),7.76(d,1H),7.64(dd,4H),7.54(dd,1H), 7.45-7.34 (m,11H),7.24(t,4H),7.20(dd,1H),7.16(dd,4H),7.11(dd,4H), 7.09-7.06 (m,4H),7.02-6.98(m,2H). The above results confirmed that the obtained product was the objective product.
Synthesis example 4: preparation of Compound 37
Figure BDA0002364918130000222
(1) To a 1.25L reaction flask were added 4- (2-benzoxazolyl) aniline (47.3g,0.225mol), bromobenzene (23.7mL,0.225mol), sodium tert-butoxide (28.8g,0.30mol), palladium acetate (2.06g,2.25mmol), tri-tert-butylphosphine (9.0mL of a 1.0M solution in toluene, 9.0mmol) and toluene (500mL) under nitrogen. The reaction was carried out under reflux for 2 hours. After the reaction is finished, cooling to room temperature, filtering the reaction solution by using kieselguhr, concentrating the filtrate, and recrystallizing by using methanol to obtain the intermediate B-1(58.0g, the yield is about 90%), wherein the solid purity is not less than 99.9% by HPLC (high performance liquid chromatography).
(2) A100 mL reaction flask was charged with intermediate B-1(17.2g,0.06mol), dibromotriphenylamine (14.4g,0.03mol), tris (dibenzylideneacetone) dipalladium (27.5mg,0.03mmol), potassium tert-butoxide (13.5g,0.12mol), tri-tert-butylphosphine (0.12mL of a 1.0M solution in toluene, 0.12mmol,1), and toluene (30mL) under argon protection, and reacted for 12 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate, and washed with saturated brine, followed by drying over anhydrous sodium sulfate. Spinning out organic solvent, eluting with petroleum ether and siliconPerforming column chromatography with gel as adsorbent, concentrating the column filtrate, and recrystallizing with methanol to obtain solid compound 37(20.3g, yield about 83%), and purity of solid is ≧ 99.9% by HPLC. Mass spectrum m/z: 813.53 (calculated value: 813.96). Theoretical element content (%) C56H39N5O2: c, 82.63; h, 4.83; n, 8.60; o, 3.93; measured elemental content (%): c, 82.76; h, 4.60; n, 8.78; and O, 3.65.1H NMR(600MHz,CDCl3And, ppm): 8.10(d,4H), 7.80-7.73 (m,2H),7.56(dd,2H), 7.41-7.30 (m,10H), 7.25-7.23 (m,4H), 7.22-7.20 (m,2H),7.16(dd,6H),7.11(s,8H),7.07(s,1H). The above results confirmed that the obtained product was the objective product.
Synthesis example 5: preparation of Compound 39
Figure BDA0002364918130000231
Compound 39(41.9g, 76%) was obtained in the same manner as in the above-mentioned synthesis example 1- (1) in which 2- (4-bromophenyl) benzoxazole was replaced with equimolar 2-phenyl-6-bromooxazole and 4- (2-benzoxazolyl) aniline in synthesis example 1- (2) was replaced with equimolar 2-phenyl-benzoxazol-6-ylamine, and the solid purity by HPLC ≧ 99.9%. Mass spectrum m/z: 930.54 (calculated value: 931.07). Theoretical element content (%) C63H42N6O3: c, 81.27; h, 4.55; n, 9.03; o, 5.16; measured elemental content (%): c, 81.33; h, 4.62; n, 9.21; and O, 5.35.1H NMR(600MHz,CDCl3And, ppm): 8.10(d,3H),8.08(d,3H),7.56 to 7.51(m,3H),7.46 to 7.39(m,9H),7.36 to 7.29(m,6H),7.24(t,4H),7.18 to 7.10(m,8H),7.09 to 7.06(m,4H),7.02 to 6.98(m,2H). The above results confirm that the product is obtained as the objective product.
Synthesis example 6: preparation of Compound 45
Figure BDA0002364918130000241
The dibromotriphenylamine in the synthesis example 4 was changed to equimolar 4,4 '-dibromo-4' -phenyltriphenylamine, and the other steps were the same, to obtainSolid compound 45(22.4g, yield about 84%), and solid purity ≧ 99.9% by HPLC. Mass spectrum m/z: 889.46 (calculated value: 890.06). Theoretical element content (%) C62H43N5O2: c, 83.67; h, 4.87; n, 7.87; o, 3.60; measured elemental content (%): c, 83.77; h, 4.67; n, 7.90; and O, 3.74. The above results confirmed that the obtained product was the objective product.
Synthesis example 7: preparation of Compound 48
Figure BDA0002364918130000242
The 2- (4-bromophenyl) benzoxazole in Synthesis example 1- (1) was changed to equimolar 9-bromophenanthrene, and the same procedures were repeated to give compound 48(42.8g, yield: 78%), and purity by HPLC ≧ 99.9%. Mass spectrum m/z: 913.44 (calculated value: 914.08). Theoretical element content (%) C64H43N5O2: c, 84.10; h, 4.74; n, 7.66; o, 3.50; measured elemental content (%): c, 84.13; h, 4.79; n, 7.74; and O, 3.66. The above results confirmed that the obtained product was the objective product.
Synthesis example 8: preparation of Compound 49
Figure BDA0002364918130000243
The dibromotriphenylamine in the synthesis example 4 is replaced by equimolar N, N-bis (4-bromophenyl) -9, 9-dimethylfluoren-2-amine, and the other steps are the same, so that the compound 49(22.6g, the yield is about 81%) is obtained, and the solid purity is not less than 99.9% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 929.47 (calculated value: 930.12). Theoretical element content (%) C65H47N5O2: c, 83.94; h, 5.09; n, 7.53; o, 3.44; measured elemental content (%): c, 84.06; h, 5.14; n, 7.69; and O, 3.54. The above results confirmed that the obtained product was the objective product.
Synthesis example 9: preparation of Compound 56
Figure BDA0002364918130000251
To a 500mL reaction flask, sodium tert-butoxide (11.5g,0.12mol), intermediate A-1(12.5g,0.024mol), N-phenyl-4-benzidine (11.8g,0.048mol), tris (dibenzylideneacetone) dipalladium (0.440g,0.48mmol), tri-tert-butylphosphine (0.48mL of a 1.0M solution in toluene, 0.48mmol), and toluene (200mL) were added under a reflux condition for 2 hours. Cooling the reaction solution, placing the reaction solution into a beaker, cooling the reaction solution in a freezer, filtering the reaction solution after 12 hours, adding acetone (100ml) into a filter cake, stirring the mixture at room temperature for 0.5 hour, filtering, drying, and recrystallizing the mixture by using methanol to obtain the solid compound 56(17.5g, the yield is 86%), wherein the purity of the solid is equal to or greater than 99.9% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 848.46 (calculated value: 849.05). Theoretical element content (%) C61H44N4O: c, 86.29; h, 5.22; n, 6.60; o, 1.88; measured elemental content (%): c, 86.32; h, 5.14; n, 6.66; o, 1.92. The above results confirmed that the obtained product was the objective product.
Synthesis example 10: preparation of Compound 64
Figure BDA0002364918130000252
Figure BDA0002364918130000261
The same procedures were repeated except for changing 2- (4-bromophenyl) benzoxazole in Synthesis example 1- (1) to equimolar 2- (4-bromophenyl) benzothiazole, changing 4- (2-benzoxazolyl) aniline in Synthesis example 1- (2) to equimolar 4- (2-benzothiazolyl) aniline, and changing bromobenzene to equimolar 4-bromobiphenyl, thereby obtaining compound 64(50.2g, 74%) with a solid purity ≧ 99.9% by HPLC. Mass spectrum m/z: 1130.29 (calculated value: 1131.45). Theoretical element content (%) C75H50N6S3: c, 79.62; h, 4.45; n, 7.43; s, 8.50; measured elemental content (%): c, 79.74; h, 4.32; n, 7.52; and S, 8.73. The above results confirmed that the obtained product was the objective product.
Synthesis example 11: preparation of Compound 65
Figure BDA0002364918130000262
The 2- (4-bromophenyl) benzoxazole in Synthesis example 1- (1) was changed to equimolar 2- (4-bromophenyl) -benzo [ B ]]Thiophene, 4- (2-benzoxazolyl) aniline in Synthesis example 1- (2) was replaced with an equimolar amount of 4- (2-benzothiazolyl) aniline, and the same procedure was repeated to give 65(41.1g, 70%) as a solid having a purity of 99.9% by HPLC. Mass spectrum m/z: 977.27 (calculated value: 978.26). Theoretical element content (%) C64H43N5S3: c, 78.58; h, 4.43; n, 7.16; s, 9.83; measured elemental content (%): c, 78.66; h, 4.31; n, 7.23; and S, 9.87. The above results confirmed that the obtained product was the objective product.
Synthesis example 12: preparation of Compound 78
Figure BDA0002364918130000271
The intermediate a-1 in synthesis example 9 was replaced with an equimolar amount of the intermediate a-5, N-phenyl-4-benzidine, and an equimolar amount of N-phenyl-2 (9, 9-dimethyl-9H-fluorene) amine, and solid compound 78(18.6g, yield 82%) was obtained in the same manner as in the other steps, and the solid purity was 99.9% or more by HPLC. Mass spectrum m/z: 944.31 (calculated value: 945.24). Theoretical element content (%) C67H52N4S: c, 85.14; h, 5.55; n, 5.93; s, 3.39; measured elemental content (%): c, 85.23; h, 5.42; n, 5.98; and S, 3.34.1H NMR(600MHz,CDCl3And, ppm): 8.09(dd,1H),8.05(dd,1H),7.80(d,2H),7.73(d,4H), 7.63-7.56 (m,3H), 7.55-7.49 (m,3H),7.48(d,1H),7.46(d,1H), 7.44-7.39 (m,4H),7.33(d,2H),7.24(t,4H),7.12(dd,4H),7.09(t, 4H)7.08(t,4H), 7.03-6.97 (m,2H), 1.71(s,12H). The above results confirm that the product is obtained as the objective product.
Synthesis example 13: preparation of Compound 79
Figure BDA0002364918130000272
The bromobenzene in synthetic example 4 was replaced with equimolar 1-bromonaphthalene, and the other steps were carried out in the same manner to obtain 79 as a solid (21.9g, yield about 80%) with a purity of 99.9% or more by HPLC. Mass spectrum m/z: 913.57 (calculated value: 914.08). Theoretical element content (%) C64H43N5O2: c, 84.10; h, 4.74; n, 7.66; o, 3.50; measured elemental content (%): c, 84.24; h, 4.68; n, 7.73; and O, 3.62.1H NMR(600MHz,CDCl3And, ppm): 8.05(d,4H),7.95(t,4H),7.86(d,2H),7.74(d,2H), 7.58-7.49 (m,6H), 7.47-7.40 (m,4H), 7.35-7.28 (m,7H),7.14(d,6H), 7.07-7.01 (m,4H),6.97(d,4H). The above results confirm that the product is obtained as the objective product.
Synthesis example 14: preparation of Compound 107
Figure BDA0002364918130000281
The intermediate B-1 in synthesis example 4 was replaced with an equimolar amount of intermediate B-6, 4,4' -dibromo-4 ″ -phenyl triphenylamine, and the same procedure was repeated to obtain a solid compound 107(20.8g, yield about 85%) with a solid purity of 99.9% or more by HPLC. Mass spectrum m/z: 813.47 (calculated value: 813.96). Theoretical element content (%) C56H39N5O2: c, 82.63; h, 4.83; n, 8.60; o, 3.93; measured elemental content (%): c, 82.75; h, 4.74; n, 8.73; and O, 3.87. The above results confirmed that the obtained product was the objective product.
Synthesis example 15: preparation of Compound 114
Figure BDA0002364918130000282
The intermediate B-1 in Synthesis example 4 was replaced with equimolar intermediate B-3, 4,4 '-dibromo-4' -phenyltriphenylamine with equimolar N, N-bis (4-bromophenyl) -9, 9-dimethylfluoren-2-amine, and the other steps were the same,to obtain the solid compound 114(22.8g, the yield is about 82%), and the solid purity is not less than 99.9% by HPLC. Mass spectrum m/z: 929.43 (calculated value: 930.12). Theoretical element content (%) C65H47N5O2: c, 83.94; h, 5.09; n, 7.53; o, 3.44; measured elemental content (%): c, 83.82; h, 5.27; n, 7.60; and O, 3.55. The above results confirmed that the obtained product was the objective product.
Synthesis example 16: preparation of Compound 116
Figure BDA0002364918130000283
By replacing intermediate a-1 in synthesis example 9 with an equimolar amount of intermediate a-3 and carrying out the same procedures, solid compound 116(17.7g, yield 87%) was obtained, and the solid purity was ≧ 99.9% by HPLC. Mass spectrum m/z: 848.56 (calculated value: 849.05). Theoretical element content (%) C61H44N4O: c, 86.29; h, 5.22; n, 6.60; o, 1.88; measured elemental content (%): c, 86.34; h, 5.16; n, 6.82; o, 1.97. The above results confirmed that the obtained product was the objective product.
Synthesis example 17: preparation of Compound 118
Figure BDA0002364918130000291
Solid compound 118(18.7g, yield 84%) was obtained in the same manner as in the above-described synthesis example 9 except that the intermediate a-1 was replaced with an equimolar amount of intermediate a-3, N-phenyl-4-benzidine and an equimolar amount of N-phenyl-2 (9, 9-dimethyl-9H-fluorene) amine, and the solid purity was 99.9% or more by HPLC. Mass spectrum m/z: 928.24 (calculated value: 929.18). Theoretical element content (%) C67H52N4O: c, 86.61; h, 5.64; n, 6.03; o, 1.72; measured elemental content (%): c, 86.82; h, 5.71; n, 6.12; o, 1.75. The above results confirmed that the obtained product was the objective product.
Synthesis example 18: preparation of Compound 131
Figure BDA0002364918130000292
Compound 131(42.8g, 73%) was obtained in the same manner as in the previous step, except that 2- (4-bromophenyl) benzoxazole in Synthesis example 1- (1) was changed to equimolar 2-phenyl-6-bromothiazole and 4- (2-benzoxazolyl) aniline in Synthesis example 1- (2) was changed to equimolar 2-phenyl-benzothiazol-6-ylamine, and the solid purity by HPLC ≧ 99.9%. Mass spectrum m/z: 978.38 (calculated value: 979.25). Theoretical element content (%) C63H42N6S3: c, 77.27; h, 4.32; n, 8.58; s, 9.82; measured elemental content (%): c, 77.31; h, 4.43; n, 8.69; and S, 9.64. The above results confirmed that the obtained product was the objective product.
Synthesis example 19: preparation of Compound 142
Figure BDA0002364918130000301
By replacing intermediate a-1 in synthesis example 9 with an equimolar amount of intermediate a-7 and carrying out the same procedures, solid compound 142(18.1g, yield 87%) was obtained, and the solid purity was ≧ 99.9% by HPLC. Mass spectrum m/z: 864.57 (calculated value: 865.11). Theoretical element content (%) C61H44N4S: c, 84.69; h, 5.13; n, 6.48; s, 3.71; measured elemental content (%): c, 84.76; h, 5.35; n, 6.57; and S, 3.86. The above results confirmed that the obtained product was the objective product.1H NMR(600MHz,CDCl3,,ppm)：7.98–7.94(m,2H),7.93(d,1H),7.74(d,1H),7.61–7.57(m,4H),7.53–7.49(m,3H),7.48–7.41(m,9H),7.38–7.31(m,6H),7.24(t,4H),7.14(d,4H),7.12–7.06(m,8H),7.02-6.98(m,2H).
Preparation of devices
Description of organic materials: the organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.
Description of the substrate: the ITO glass substrate was purchased from shenzhen south glass display technology ltd. The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C.
Description of vapor deposition System: the device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an SQM160 quartz crystal film thickness detector of Inficon, and detecting the film thickness by using a quartz crystal oscillator.
Description of the test System: the driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device are tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states into a combined IVL test system.
Example 1: preparation of organic electroluminescent device 1
ITO is used as an anode on a glass substrate; HAT-CN is evaporated on the anode in vacuum to be used as a hole injection layer, and the evaporation thickness is 5 nm; performing vacuum evaporation on the hole on the injection layer to form an HTM-1 layer as a first hole transport layer, wherein the evaporation thickness is 60 nm; vacuum evaporating the compound 1 of the invention on the first hole transport layer to form a second hole transport layer, wherein the evaporation thickness is 5 nm; evaporating mCBP Ir (ppy) on the second hole transport layer in vacuum3(95:5) vapor deposition of a light-emitting layer having a thickness of 20 nm; performing vacuum evaporation on the luminescent layer to form ETM-1: LiQ (50:50) as an electron transport layer, wherein the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; al is vacuum-evaporated on the electron injection layer to form a cathode, and the thickness of the vapor-deposited layer is 100 nm.
Examples 2 to 10: the compound 1 in the second hole transport layer in example 1 was replaced with the compound 6, the compound 37, the compound 48, the compound 56, the compound 64, the compound 79, the compound 107, the compound 112, and the compound 116, respectively, and the same procedure was repeated to obtain organic electroluminescent devices 2 to 10.
Comparative examples 1 to 4: the compounds in the second hole transport layer in example 1 were replaced with compound R-1, compound R-2, compound R-3, and compound R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 4.
Figure BDA0002364918130000311
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 10 of the present invention and comparative examples 1 to 4 are shown in table 1.
Table 1 test data of light emitting characteristics of organic electroluminescent device
Figure BDA0002364918130000312
Figure BDA0002364918130000321
As can be seen from table 1, the devices of examples 1 to 10 have higher light emitting efficiency than the devices of comparative examples 1 to 4, because the triamine derivative of the present invention can better block electrons when being used as a hole transport material, and effectively limits a part of electrons from migrating into the hole transport layer through the light emitting layer, so that holes and electrons can be effectively combined in the light emitting layer to form excitons, thereby improving the light emitting efficiency of the devices.
Example 11: preparation of organic electroluminescent device 11
ITO/Ag/ITO is used as an anode on the glass substrate; NPB: F4-TCNQ (97:3) is evaporated on the anode in vacuum to be used as a hole injection layer, and the evaporation thickness is 40 nm; carrying out vacuum evaporation on the NPB on the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 50 nm; vacuum evaporation of BH-1: BD-1(97:3) as emission onto the hole transport layerAn optical layer with a vapor deposition thickness of 20 nm; vacuum evaporation of Alq on the luminescent layer3As an electron transport layer, the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; vacuum evaporating Mg/Ag (9:1) on the electron injection layer to form a cathode, wherein the evaporation thickness is 15 nm; the compound 2 of the present invention was vacuum-deposited on the cathode as a light extraction layer to a thickness of 60 nm.
Examples 12 to 15: in example 11, the compound 2 in the light extraction layer was replaced with the compound 39, the compound 65, the compound 82, the compound 114, the compound 123, and the compound 131, and the same procedure was followed to obtain organic electroluminescent devices 12 to 17.
Comparative examples 5 to 7: the compound 2 in the light extraction layer in example 11 was replaced with a compound HTM-1, a compound R-1, and a compound R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 5 to 7.
Example 18: ITO/Ag/ITO is used as an anode on the glass substrate; NPB: F4-TCNQ (97:3) is evaporated on the anode in vacuum to be used as a hole injection layer, and the evaporation thickness is 40 nm; carrying out vacuum evaporation on the NPB on the hole injection layer to form a first hole transmission layer, wherein the evaporation thickness is 50 nm; vacuum evaporating the compound 45 of the invention on the first hole transport layer to form a second hole transport layer, wherein the evaporation thickness is 5 nm; vacuum evaporating BH-1: BD-1(97:3) on the second hole transport layer to be used as a light emitting layer, wherein the evaporation thickness is 20 nm; vacuum evaporation of Alq on the luminescent layer3As an electron transport layer, the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; vacuum evaporating Mg/Ag (9:1) on the electron injection layer to form a cathode, wherein the evaporation thickness is 15 nm; the compound 11 of the present invention was vacuum-deposited on the cathode as a light extraction layer to a thickness of 60 nm.
Examples 19 to 24: the compound 45 in the second hole-transporting layer in example 18 was replaced with a compound 48, a compound 107, a compound 108, a compound 114, a compound 116, a compound 131; and respectively replacing the compound 11 in the light extraction layer with a compound 45, a compound 49, a compound 78, a compound 108, a compound 118 and a compound 142, and obtaining the organic electroluminescent devices 19-24 by the same steps.
Comparative examples 8 to 9: the compound 45 in the second hole transport layer in example 18 was replaced with a compound R-2 and a compound R-4, respectively; and respectively replacing the compound 11 in the light extraction layer with a compound HTM-1 and a compound R-3, and obtaining the comparative organic electroluminescent devices 8-9 by the same steps.
Figure BDA0002364918130000331
The results of the tests on the light emitting characteristics of the organic electroluminescent devices prepared in examples 11 to 24 and comparative examples 5 to 9 of the present invention are shown in table 2.
Table 2 light emitting characteristic test data of organic electroluminescent device
Figure BDA0002364918130000332
Figure BDA0002364918130000341
As can be seen from Table 2, the devices of examples 11 to 17 have significantly improved luminous efficiencies as compared with the devices of comparative examples 5 to 7, since the triamine derivatives of the present invention can efficiently couple out light trapped in the devices when used as light extraction materials, and thus the luminous efficiencies of the devices are greatly improved. The devices of examples 18 to 24 have higher luminous efficiency than the devices of comparative examples 8 to 9, because the triamine derivative of the present invention has not only better light extraction performance but also better hole mobility and electron blocking function, and when the triamine derivative is used for the light extraction layer and the hole transport layer of the organic electroluminescent device, the luminous efficiency of the device can be significantly improved, and the triamine derivative is an organic photoelectric material with good performance.

Claims (9)

1. A triamine derivative is characterized in that the triamine derivative is shown as a formula I,
Figure FDA0002786784680000011
wherein, Ar and Ar are1、Ar2、Ar3、Ar4Independently selected from one of the groups shown in the following,
Figure FDA0002786784680000012
and, Ar1、Ar2At least one of which is selected from one of the groups shown below,
Figure FDA0002786784680000013
x is selected from O or S; the L is selected from one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted furylene and substituted or unsubstituted thienylene;
r is selected from one of hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted furyl and substituted or unsubstituted thienyl;
the R is0One selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl; the substitution means that hydrogen in a certain group is replaced by another substituent group, and the substituent group is selected from one or more of the following groups: deuterium, halogen atom, cyano, C1-C15 alkyl, C6-C30 aryl or C3 to C30.
2. The triamine derivative according to claim 1, wherein Ar is selected from one of the following groups,
Figure FDA0002786784680000014
Figure FDA0002786784680000021
3. the triamine derivative according to claim 1, wherein the triamine derivative is selected from one of the following formulas I-1 to I-5,
Figure FDA0002786784680000022
Figure FDA0002786784680000031
wherein Ar is selected from one of the groups shown in the specification,
Figure FDA0002786784680000032
4. the triamine derivative of claim 3 wherein the Ar is3、Ar4Independently selected from one of the groups shown in the following,
Figure FDA0002786784680000033
5. the triamine derivative of claim 4 wherein the Ar is3、Ar4Independently selected from one of the groups shown in the following,
Figure FDA0002786784680000034
6. the triamine derivative of claim 1 wherein the triamine derivative is selected from one of the following structures,
Figure FDA0002786784680000041
Figure FDA0002786784680000051
Figure FDA0002786784680000061
Figure FDA0002786784680000071
Figure FDA0002786784680000081
Figure FDA0002786784680000091
Figure FDA0002786784680000101
Figure FDA0002786784680000111
7. an organic electroluminescent device comprising an anode, a light-emitting layer and a cathode, wherein the light-emitting layer is located between the anode and the cathode, and further comprising at least one of a hole transport layer and a light extraction layer, wherein the hole transport layer is located between the anode and the light-emitting layer, the light extraction layer is located on the side of the cathode away from the anode, and the hole transport layer or the light extraction layer comprises the triamine derivative according to any one of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, further comprising a hole transport layer comprising a first hole transport layer and a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the light-emitting layer, the second hole transport layer comprising the triamine derivative according to any one of claims 1 to 6.
9. The organic electroluminescent device according to claim 7, further comprising a light extraction layer containing the triamine derivative according to any one of claims 1 to 6.
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