WO2021114802A1 - 一种四齿铂(ii)配合物的制备及应用 - Google Patents

一种四齿铂(ii)配合物的制备及应用 Download PDF

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WO2021114802A1
WO2021114802A1 PCT/CN2020/116336 CN2020116336W WO2021114802A1 WO 2021114802 A1 WO2021114802 A1 WO 2021114802A1 CN 2020116336 W CN2020116336 W CN 2020116336W WO 2021114802 A1 WO2021114802 A1 WO 2021114802A1
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康健
戴雷
蔡丽菲
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广东阿格蕾雅光电材料有限公司
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Priority to KR1020227013152A priority Critical patent/KR20220065849A/ko
Priority to JP2022531548A priority patent/JP7385754B2/ja
Priority to DE112020004793.8T priority patent/DE112020004793T5/de
Priority to US17/776,937 priority patent/US20230006154A1/en
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Definitions

  • the present invention relates to a new type of tetradentate platinum (II) complex metal organic material, in particular to a phosphorescent doped material used for photon emission in the light-emitting layer of an OLED light-emitting device.
  • II tetradentate platinum
  • OLED Organic Light-Emitting Diode
  • LCD Liquid Crystal Display, liquid crystal display
  • OLED display technology is self-luminous, wide viewing angle, almost infinitely high contrast, low power consumption, extremely high response speed and potential flexible foldable
  • OLEDs based on organic materials have many irreplaceable superior properties.
  • the main reasons are: (1) Organic materials are easy to form films on any substrate and can be manufactured. Into ultra-thin flat panel display panels; (2) The organic molecular structure can be designed to adjust the luminescence properties of materials, which is easy to modify and reform; (3) The fluorescence quantum efficiency of organic luminescent materials is high, almost reaching 100%; (4) Based on Inorganic LEDs are point light sources, while OLED panels based on organic materials can produce surface light sources; (5) Organic electroluminescent OLED devices have relatively low driving voltages, while inorganic LEDs generally have relatively high driving voltages.
  • the transition metal phosphorescent materials are mainly doped as the light-emitting layer for photon emission, and the most researched ones are based on the complexes of iridium (III) and platinum (II).
  • the metal complex formed by the bidentate ligand and trivalent iridium has an octahedral coordination structure, and the iridium atom is located in the center of the octahedron to chelate and coordinate with the bidentate ligand.
  • iridium (III) complexes may produce isomers. Due to the different coordination orientations of the ligands, there are two structures of plane and meridian, resulting in iridium (III) complexes. The separation difficulty increases and the yield of the target iridium(III) complex decreases.
  • platinum (II)-based phosphorescent OLED materials have gradually developed and achieved good research results in recent years.
  • platinum (II) is four-coordinated, so it generally forms a complex with a planar structure.
  • Common ligands are mainly divided into bidentate, tridentate and tetradentate ligands. . Compared with bidentate or tridentate ligands, tetradentate platinum(II) complexes have the following advantages:
  • the platinum(II) complex can be synthesized by one step reaction of the ligand, which is easy to prepare and purify the platinum(II) complex;
  • the tetradentate ligand platinum(II) complex has attracted more research and attention due to its unique properties.
  • the research team of Academician Zhiming Zhi from the University of Hong Kong has conducted in-depth research on such complexes and achieved excellent results. (Chem. Sci. 2016, 7, 1653).
  • the tetradentate ligand-like platinum(II) complexes show good performance. At the same time, due to the planar structure of the platinum(II) complexes, it also leads to easy stacking between molecules, easy formation of excimer complexes, etc., which reduces OLED devices. Performance.
  • This application provides a novel Pt(II) complex based on a tetradentate ligand, which emits green light and is used as a green phosphorescent OLED material in OLED devices.
  • This new type of Pt(II) complex has an ONCN chelating coordination model, and has a spiro structure on the molecular skeleton. This structure greatly enhances the three-dimensionality of the molecule, which is beneficial to weaken the interaction between molecules and avoid complexes. Molecular stacking inhibits the formation of excimer associations, and improves the efficiency and lifetime of OLED devices.
  • novel tetradentate platinum (II) complex metal organic material involved in the present invention has a structure shown in the following formula:
  • R 1 -R 21 are independently selected from hydrogen, deuterium, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carbamoyl, benzylcarbonyl, aryloxy, diarylamino, silyl group containing 1-30 C atoms, saturated alkyl group containing 1-30 C atoms, unsaturated alkyl group containing 2-20 C atoms Alkyl group, substituted or unsubstituted aryl group containing 5-30 C atoms, substituted or unsubstituted heteroaryl group containing 5-30 C atoms, or adjacent R 1 -R 21 are mutually covalent
  • the bond is connected to form a ring, wherein the substitution is substituted by halogen, deuterium, C1-C20 alkyl, and cyano, and the heteroatom in the heteroaryl group is one or more of
  • R 1 -R 21 are independently selected from hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl containing 1-10 C atoms, halogenated or one or more C1- C4 alkyl substituted or unsubstituted aryl groups containing 5-20 C atoms, halogen or one or more C1-C4 alkyl substituted or unsubstituted heteroaryl groups containing 5-20 C atoms, Or adjacent R 1 -R 21 are connected to each other through a covalent bond to form a ring, and the halogen is F, Cl, or Br.
  • 0 to 3 groups are independently represented as diarylamino groups, substituted or unsubstituted by halogen or 1 to 3 C1-C4 alkyl groups
  • 0 to 3 groups are independently represented as diphenylamino, phenyl, pyridyl, carbazolyl, and other groups are independently represented as Hydrogen, fluorine or saturated alkyl with 1 to 4 C atoms
  • R 1 '-R 6' is independently selected from hydrogen, halogen, di-arylamino, saturated alkyl group containing 1-10 C atoms, with one or more halogen or C1-C4 alkyl substituted or unsubstituted an aryl group containing 5-20 C atoms, with one or more halogen or C1-C4 alkyl substituted or unsubstituted heteroaryl containing 5 to 20 C atoms of an aryl group, or adjacent R 1 '-R 6 'are connected to each other by a covalent bond to form a ring, said halogen is F, Cl, Br, the heteroaryl group is any heteroatoms N, O, S in eleven kinds.
  • R 1 '-R 6' 6 groups which groups with 0-3 independently represent diarylamino group, halogen or 1-3 C1-C4 alkyl substituted or unsubstituted Substituted aryl groups containing 5-10 C atoms, heteroaryl groups containing 5-10 C atoms substituted or unsubstituted by halogen or 1 to 3 C1-C4 alkyl groups; other groups are independently represented It is hydrogen, halogen or saturated alkyl containing 1-8 C atoms, and the halogen is F, Cl.
  • R 1 '-R 6' 6 groups which independently have 0-3 groups expressed as diphenylamino, C1-C4 alkyl substituted or unsubstituted phenyl, pyridyl, carbazole
  • the azole group and other groups are independently represented by hydrogen, fluorine, and saturated alkyl containing 1 to 4 C atoms.
  • halogen alkyl, alkenyl, aryl, acyl, alkoxy, and heterocyclic aromatic systems or heterocyclic aromatic groups may have the following meanings:
  • halogen or halo includes fluorine, chlorine, bromine and iodine, preferably F, Cl, Br, particularly preferably F or Cl, and most preferably F.
  • the above-mentioned covalent bond to form a ring, aryl, and heteroaryl include groups having 5-30 carbon atoms, preferably 5-20 carbon atoms, more preferably 5-10 carbon atoms and composed of one aromatic ring or multiple fused
  • the aromatic ring consists of the aryl group.
  • Suitable aryl groups are, for example, phenyl, naphthyl, acenaphthenyl, acenaphthenyl, anthracenyl, fluorenyl, phenalenyl.
  • the aryl group may be unsubstituted (that is, all carbon atoms that can be substituted carry hydrogen atoms) or substituted at one, more than one, or all substitutable positions of the aryl group.
  • Suitable substituents are, for example, halogen, preferably F, Br or Cl; alkyl groups, preferably alkyl groups having 1-20, 1-10 or 1-8 carbon atoms, particularly preferably methyl, ethyl, isopropyl Aryl group or tert-butyl group; aryl group, preferably a C 5 , C 6 aryl group or fluorenyl group that can be substituted again or unsubstituted; heteroaryl group, preferably a heteroaryl group containing at least one nitrogen atom, particularly preferably a pyridyl group;
  • the aryl group particularly preferably has a substituent selected from the group consisting of F, methyl and tert-butyl, or an aryl group optionally substituted
  • the unsaturated alkyl group containing 1-20 C atoms is preferably an alkenyl group, more preferably an alkenyl group having a double bond, and particularly preferably an alkenyl group having a double bond and 1-8 carbon atoms.
  • the above-mentioned alkyl group includes an alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and preferably 1 to 4 carbon atoms.
  • the alkyl group may be branched or linear, or cyclic, and may be interrupted by one or more heteroatoms, preferably N, O or S.
  • the alkyl group may be substituted with one or more halogens or the above-mentioned substituents with respect to the aryl group.
  • Alkyl groups are particularly preferably selected from methyl, ethyl, isopropyl, n-propyl, Isobutyl, n-butyl, tert-butyl, sec-butyl, isopentyl, cyclopropyl, cyclopentyl, cyclohexyl.
  • acyl group is a single bond attached to the CO group, such as an alkyl group as used herein.
  • alkoxy group is directly connected to oxygen by a single bond, such as the alkyl group used herein.
  • heteroaryl groups are understood to be related to aromatic, C 3 -C 8 cyclic groups, and also contain one oxygen or sulfur atom or 1 to 4 nitrogen atoms or a combination of one oxygen or sulfur atom and up to two nitrogen atoms , And their substituted and benzo- and pyrido-fused derivatives, for example, via one of the ring-forming carbon atoms, the heteroaryl group may be substituted by one or more of the mentioned aryl substituents Replaced.
  • the heteroaryl group may be a five- or six-membered aromatic heterocyclic ring system with independent 0, 1, or 2 substituents.
  • Typical examples of heteroaryl groups include, but are not limited to, unsubstituted furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, azole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzo Thiazole, isothiazole, imidazole, benzimidazole, pyrazole, indazole, tetrazole, quinoline, isoquinoline, pyridazine, pyrimidine, purine and pyrazine, furan, 1,2,3-diazole, 1, 2,3-thiadiazole, 1,2,4-thiadiazole, triazole, benzotriazole, pteridine, benzoxazole, diazole, benzopyr
  • the substituents are halo, hydroxy, cyano, OC 1-6 alkyl, C 1-6 alkyl, hydroxy C 1-6 alkyl, and amino-C 1-6 alkyl.
  • the specific examples shown below include but are not limited to the following structures:
  • the complex is applied in the form of a layer in the device by thermal deposition.
  • the complex is applied in the form of a layer in the device by spin coating.
  • the complex is applied in the form of a layer in the device by inkjet printing.
  • the above-mentioned organic light-emitting device emits orange-red when a current is applied.
  • the organometallic complex in the present invention has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can manufacture orange-red light OLED devices with high luminous efficiency and low roll-off.
  • Fig. 1 is a schematic diagram of the structure of the organic electroluminescent device of the present invention.
  • the preparation method of the above complex includes the following steps:
  • the initial substrates S1 and S2 undergo Suzuki-Miyaura coupling reaction to obtain substrate S3, S3 and S4 undergo Buchwald–Hartwig coupling reaction to obtain substrate S5, and S5 and S6 undergo Buchwald–Hartwig coupling reaction to obtain substrate S3.
  • S7 and S7 are demethylated by heating at high temperature under the action of pyridine hydrochloride to obtain S8, and S8 is chelated with K 2 PtCl 4 to obtain the target platinum (II) complex TM.
  • the initial substrates, intermediates, solvents and other reagents involved in the synthesis of the compounds of the present invention are all purchased from suppliers well-known to those skilled in the art, such as Anegie, Braunschweiler, Aladdin and the like.
  • Synthesis of compound 3 Take 20.0g (0.10mol) of compound 1, 19.8g (0.125mol) of compound 2, 3.46g (0.03eq., 3.0mmol) of tetrakis (triphenylphosphine) palladium, 27.6g (2.0eq) of potassium carbonate ., 0.20mol) in the flask, add 210mL of dioxane, 60mL of water under the protection of nitrogen heated to reflux for 8 hours.
  • Synthesis of compound 7 Take 4.9g (20mmol) of compound 5, 7.9g (20mmol) of compound 6, 225mg (0.02eq., 1mmol) of palladium acetate, 0.20g (0.04eq., 2mmol) of tri-tert-butylphosphine, and tert-butyl Potassium alkoxide 4.5g (2.0eq., 0.04mol) was put in the flask, 100mL toluene was added, and the reaction was heated and refluxed for 8 hours under the protection of nitrogen.
  • the transparent anodized indium tin oxide (ITO) (10 ⁇ /sq) glass substrate was ultrasonically cleaned with acetone, ethanol and distilled water in turn, and then treated with oxygen plasma for 5 minutes.
  • ITO indium tin oxide
  • the ITO substrate was mounted on the substrate holder of the vacuum vapor deposition equipment.
  • the pressure of the control system is 10 -6 torr.
  • HTL hole transport layer
  • the light-emitting layer material (EML) TCTA with a thickness of 40 nm is evaporated, and the platinum (II) complex is doped with 10% mass fraction.
  • the electron transport layer (ETL) material TmPyPb with a thickness of 30 nm is evaporated.
  • LiF with a thickness of 1 nm is evaporated as the electron injection layer (EIL).
  • the device STD, device 1, device 2, device 3, and device 4 are sequentially prepared.
  • the structure and manufacturing method of the device are exactly the same.
  • the difference is that the platinum (II) complexes STD, Pt-1, Pt-2, Pt-3, Pt-12 is used as a dopant in the light-emitting layer.
  • the reference material STD is a classic green light material with an ONCN coordination structure.
  • the performance of the organic electroluminescent device prepared based on the platinum(II) complex of the present invention has different degrees of performance improvement compared to the benchmark device.
  • This new type of Pt(II) complex has strong molecular stericity and weak intermolecular interaction, which avoids the stacking of complex molecules on each other, greatly inhibits the formation of excimer complexes, and improves the efficiency of OLED devices.
  • the performance of the organic electroluminescent device prepared by the present invention has a better performance improvement compared with the reference device, and the involved new tetradentate platinum (II) complex metal organic material has greater application value.

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Abstract

本发明涉及一种新型四齿铂(II)配合物的制备及应用，属于OLED有机电致发光材料领域。本发明配合物具有如下结构式,用于OLED发光器件的发光层中起光子发射作用的磷光掺杂材料。本发明中的配合物具有高荧光量子效率，良好的热稳定性及低淬灭常数，可以制造高发光效率、低滚降的绿光OLED器件。

Description

一种四齿铂(II)配合物的制备及应用 技术领域
本发明涉及一种新型的四齿铂(II)配合物金属有机材料，尤其是用于OLED发光器件的发光层中起光子发射作用的磷光掺杂材料。
背景技术
有机发光二极管(Organic Light-Emitting Diode,OLED)又称为有机电激光显示、有机发光半导体，由美籍华裔科学家邓青云(Ching W.Tang)教授于1987年在柯达公司实验室中发现(Appl.Phys.Lett.1987,51,913)。相对于传统的的LCD(Liquid Crystal Display，液晶显示)显示技术，OLED显示技术因其具有自发光、广视角、几乎无穷高的对比度、较低耗电、极高反应速度以及潜在的柔性可折叠等优点，一直受到广泛的关注与研究，其中，开发新型OLED材料一直是OLED技术研究的重点与难点。
与基于无机材料的LED(Light-Emitting Diode,发光二极管)相比，基于有机材料的OLED具有许多不可替代的优越性能，主要原因在于：(1)有机材料容易在任何基板上成膜,可以制成超薄平板显示面板；(2)有机分子结构可以经过分子设计来调控材料的发光性能，易于修饰和改造；(3)有机发光材料的荧光量子效率高，几乎达到100％；(4)基于无机材料的LED是点光源，而基于有机材料的OLED面板则可以制备面光源；(5)有机电致发光的OLED器件驱动电压比较低，而无机LED驱动电压一般较高。
当前OLED材料中，作为发光层掺杂起光子发射作用的主要是过渡金属类磷光材料，其中研究较多的是基于铱(III)和铂(II)配合物类。一般而言，二齿配体与三价铱形成的金属配合物呈八面体配位结构，铱原子处于八面体中心与二齿配体螯合配位。铱(III)配合物的八面体配位结构使其具分子具有较强的立体性，避免配合物分子之间互相堆叠，在制备OLED器件过程中，高浓度掺杂时不易形成激基缔合物发光。但是，对于一些非对称二齿配体，铱(III)配合物可能会产生异构体，会因为配体配位取向不同而存在面式和经式两种结构，导致铱(III)配合物分离难度提升以及目标铱(III)配合物的产率降低。
在铱(III)配合物磷光材料不断突破的同时，近些年来基于铂(II)的磷光OLED材料在逐步发展并取得了较好的研究成果。与常见的铱(III)形成八面体配位结构不同，铂(II)为四配位，因而一般形成平面结构的配合物，常见的配体主要分为二齿，三齿和四齿配体。与二齿或者三齿配体相比，四齿配体铂(II)配合物具有以下优点：
1)由配体一步反应即可合成铂(II)配合物，易于铂(II)配合物的制备与纯化；
2)合成铂(II)配合物过程中无异构体生成，结构专一；
3)螯合配位，结构稳定；
4)具有相对较好的磷光发射效率。
四齿配体铂(II)配合物因其独特的性能，吸引了较多的研究与关注，尤其是香港大学支志明院士课题组对此类配合物进行了深入的研究并取得了优异的成果(Chem.Sci.2016,7,1653)。
四齿配体类铂(II)配合物表现出良好的性能同时，由于铂(II)配合物平面结构的特性，也导致其分子间易堆叠，易形成激基缔合物等，降低OLED器件的性能。
发明内容
本申请提供一种基于四齿配体类新型Pt(II)配合物,其呈绿光发射并作为绿光磷光OLED材料应用于OLED器件中。这类新型Pt(II)配合物具有ONCN螯合配位模型，并在分子骨架上具有螺环结构，这种结构大大增强了分子的立体性，有利于减弱分子间的相互作用，避免配合物分子堆叠，抑制激基缔合物的形成，提高OLED器件的效率和寿命。
本发明所涉及的新型的四齿铂(II)配合物金属有机材料，具有如下式所示的结构：
Figure PCTCN2020116336-appb-000001
其中R 1－R 21独立的选自氢、氘、硫、卤素、羟基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲酰基、苄基羰基、芳氧基、二芳胺基、含1－30个C原子的硅烷基、含1－30个C原子的饱和烷基、含2－20个C原子的不饱和烷基、取代的或未取代的含5－30个C原子的芳基、取代的或未取代的含5－30个C原子的杂芳基、或者相邻R 1－R 21相互通过共价键连接成环，其中取代为被卤素，氘、C1-C20烷基、氰基取代，所述杂芳基中杂原子为N、O、S中的一个或多个。
优选：其中R 1－R 21独立的选自氢、卤素、氨基、硝基、氰基、二芳胺基、含1－10个C原子的饱和烷基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的芳基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的杂芳基、或者相邻R 1－R 21相互通过共价键连接成环,所述卤素为F，Cl，Br。
优选：其中R 1－R 21的21个基团中，其中有0－3个基团独立的表示为二芳胺基、被卤素 或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的芳基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的含N杂芳基；其它的基团独立的表示为氢或含1－8个C原子的饱和烷基,所述卤素为F，Cl。
优选：其中所述R 1－R 21的21个基团中，其中有0－3个基团独立的表示为二苯胺基、苯基、吡啶基、咔唑基，其它基团独立的表示为氢、氟或者1－4个C原子的饱和烷基。
Figure PCTCN2020116336-appb-000002
其中R 1’－R 6’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的芳基、被卤素或一个或多个C1－C4烷基取代的或未取代杂的含5－20个C原子的芳基、或者相邻R 1’－R 6’相互通过共价键连接成环，所述卤素为F，Cl，Br，所述杂芳基中杂原子为N、O、S中的任一一种。
优选：其中R 1’－R 6’的6个基团中，其中有0－3个基团独立的表示为二芳胺基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的芳基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的杂芳基；其它的基团独立的表示为氢、卤素或含1－8个C原子的饱和烷基，所述卤素为F，Cl。
优选：其中R 1’－R 6’的6个基团中，其中有0－3个基团独立的表示为二苯胺基、C1-C4烷基取代或未取代的苯基、吡啶基、咔唑基，其它基团独立的表示为氢、氟、含1－4个C原子的饱和烷基。
上述配合物的前体，如下式所示：
Figure PCTCN2020116336-appb-000003
为了本申请的目的，除非另有指明，术语卤素、烷基、烯基、芳基、酰基、烷氧基和杂环芳族体系或杂环芳族基团可有以下含义：
上述卤素或卤代包括氟、氯、溴和碘，优选F，Cl，Br，特别优选F或Cl，最优选F。
上述通过共价键连接成环、芳基、杂芳基包括具有5－30个碳原子，优选5－20个碳原子，更优选5－10个碳原子并且由一个芳环或多个稠和的芳环组成的芳基。适宜的芳基为，例如苯基，萘基，苊基(acenaphthenyl)，二氢苊基(acenaphthenyl)，蒽基、芴基、菲基(phenalenyl)。该芳基可为未取代的(即所有能够取代的碳原子带有氢原子)或在芳基的一个、多于一个或所有可取代的位置上被取代。适宜的取代基为例如卤素，优选F、Br或Cl；烷基，优选具有1－20个，1－10个或1－8个碳原子的烷基，特别优选甲基、乙基、异丙基或叔丁基；芳基，优选可再次被取代的或是未取代C 5，C 6芳基或芴基；杂芳基，优选含至少一个氮原子的杂芳基，特别优选吡啶基；芳基尤其特别优选带有选自F，甲基和叔丁基的取代基，或任选被至少一个上述取代基取代的为C 5，C 6芳基的芳基，C 5，C 6芳基特别优选带有0、1或2个上述取代基，C 5，C 6芳基尤其特别优选未取代的苯基或取代的苯基，诸如联苯基、被两个叔丁基优选在间位取代的苯基。
含1－20个C原子的不饱和烷基，优选烯基，更优选具有一个双键的烯基，特别优选具有双键和1－8个碳原子的烯基。
上述烷基包括具有1－30个碳原子，优选1－10个碳原子，优选1－4个碳原子的烷基。该烷基可为支链或直链的，也可以是环形的，并且可被一个或多个杂原子，优选N、O或S间断。而且，该烷基可被一个或多个卤素或上述的关于芳基的取代基所取代。同样，对于烷基而言，带有一个或多个芳基是可能的，所有上述的芳基均适用于该目的，烷基特别优选自甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、仲丁基、异戊基、环丙基、环戊基、环己基。
上述酰基是以单键连接至CO基团的，如本文所用的烷基。
上述烷氧基是以单键与氧直接相连的，如本文所用的烷基。
上述杂芳基团被理解为与芳族、C 3－C 8环基相关，并且还包含一个氧或硫原子或1－4个氮原子或一个氧或硫原子与最多两个氮原子的组合，和他们的取代的以及苯并和吡啶并稠和的衍生物，例如，经由其中一个成环碳原子相连，所述杂芳基团可被一个或多个提到的关于芳基的取代基所取代。
在某些实施方案中，杂芳基可为携带以上独立的含有0、1或2个取代基的五、六元芳族杂环体系。杂芳基的典型实例包括但不限于未取代的呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡啶、吲哚、唑、苯并唑、异唑、苯并异唑、噻唑、苯并噻唑、异噻唑、咪唑、苯并咪唑、吡唑、吲唑、四唑、喹啉、异喹啉、哒嗪、嘧啶、嘌呤和吡嗪、呋喃、1,2,3-二唑、1,2,3-噻二唑、1,2,4-噻二唑、三唑、苯并三唑、喋啶、苯并唑、二唑、苯并吡唑、喹嗪、噌啉、酞嗪、喹唑和喹喔啉及其单-或二-取代的衍生物。在某些实施方案中，取代基为卤代、羟基、 氰基、O-C 1～6烷基、C 1～6烷基、羟基C 1～6烷基和氨基-C 1～6烷基。如下所示的具体实例，包括但不限于以下结构：
Figure PCTCN2020116336-appb-000004
Figure PCTCN2020116336-appb-000005
Figure PCTCN2020116336-appb-000006
上述配合物在OLED发光器件中的应用。
采用具有上述结构的铂(II)配合物，可制造热沉积和溶液处理的OLED器件。
包括含有一种或多种上述配合物的有机发光器件。
其中通过热沉积在该器件中以层形式施加该配合物。
其中通过旋涂在该器件中以层形式施加该配合物。
其中通过喷墨打印在该器件中以层形式施加该配合物。
上述有机发光器件，在施加电流时该器件发射为橙红色。
本发明中的有机金属配合物具有高荧光量子效率，良好的热稳定性及低淬灭常数，可以制造高发光效率、低滚降的橙红色光OLED器件。
附图说明
图1本发明的有机电致发光器件的结构示意图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明。
上述配合物的制备方法，包括如下步骤：
如下所示，初始底物S1与S2经Suzuki-Miyaura偶联反应得到底物S3，S3与S4经Buchwald–Hartwig偶联反应得到底物S5，S5与S6经Buchwald–Hartwig偶联反应得到底物S7,S7在吡啶盐酸盐作用下高温加热脱甲基得到S8，S8与K 2PtCl 4螯合反应即得到目标铂(II)配合物TM。
Figure PCTCN2020116336-appb-000007
本发明中化合物合成中涉及的初始底物，中间体和溶剂等试剂均购自安耐吉，百灵威，阿拉丁等本领域技术人员熟知的供应商。
实施例1：
Figure PCTCN2020116336-appb-000008
化合物3的合成：取20.0g(0.10mol)化合物1，19.8g(0.125mol)化合物2，四(三苯基膦)钯3.46g(0.03eq.,3.0mmol)，碳酸钾27.6g(2.0eq.,0.20mol)于烧瓶中，加入210mL二氧六环，60mL水在氮气保护下加热回流反应8小时。停止反应后，冷却至室温旋蒸除去溶剂，加入适量水和乙酸乙酯萃取，收集有机相并干燥，旋蒸除去溶剂后使用快速 硅胶色谱柱(流动相正己烷/乙酸乙酯＝10：1)分离再重结晶得到20.0g目标产物化合物3，产率85％，纯度99.9％。
化合物5的合成：取11.7g(50mmol)化合物3，9.3g(50mmol)化合物4，醋酸钯450mg(0.04eq.,2mmol)，三叔丁基膦0.40g(0.08eq.,4mmol)，叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中，加入200mL甲苯，在氮气保护下加热回流反应8小时。停止反应后，冷却至室温旋蒸除去溶剂，加入适量水和乙酸乙酯萃取，收集有机相并干燥，旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯＝15：1)分离再重结晶得到23.83g目标产物化合物5，产率88％，纯度99.9％。
化合物7的合成：取4.9g(20mmol)化合物5，7.9g(20mmol)化合物6，醋酸钯225mg(0.02eq.,1mmol)，三叔丁基膦0.20g(0.04eq.,2mmol)，叔丁醇钾4.5g(2.0eq.,0.04mol)于烧瓶中，加入100mL甲苯，在氮气保护下加热回流反应8小时。停止反应后，冷却至室温旋蒸除去溶剂，加入适量水和乙酸乙酯萃取，收集有机相并干燥，旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯＝10：1)分离再重结晶得到8.9g目标产物化合物7，产率75％，纯度99.9％。
化合物8的合成：取5.9g(10mmol)化合物7，吡啶盐酸盐50g，在氮气保护下加热至200℃反应8小时。停止反应后，加入适量水和乙酸乙酯萃取，收集有机相并干燥，旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯＝15：1)分离,再使用甲醇重结晶得到目标产物化合物8 5.0g，产率86％，纯度99.9％。质谱(ESI -)([M-H] -)C 41H 27N 3O理论值:576.22；实测值:576.21。
化合物Pt-1的合成：取1.15g(2.0mmol)化合物8,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol)，溶于50mL乙酸中，抽真空通入氮气置换数次，搅拌加热至130℃反应12hrs。反应结束后，冷却旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后旋蒸除去溶剂，使用使用快速硅胶色谱柱(流动相正己烷/二氯甲烷＝10：1)分离,再使用甲醇重结晶，将得到的粗品真空升华得到红色固体616mg，总产率40％，纯度99.95％。质谱(ESI -)([M+H] -)C 41H 25N 3OPt理论值:771.16；实测值:771.19。
实施例2：
Figure PCTCN2020116336-appb-000009
Pt-2制备方法与Pt-1的合成路线相同，唯一区别是使用化合物9替代化合物4。化合物9的分子式如下所示：
Figure PCTCN2020116336-appb-000010
实施例3：
Figure PCTCN2020116336-appb-000011
Pt-3制备方法与Pt-1的合成路线相同，唯一区别是使用化合物9替代化合物4，化合物10代替化合物6。化合物10的分子式如下所示：
Figure PCTCN2020116336-appb-000012
实施例4：
Figure PCTCN2020116336-appb-000013
Pt-12制备方法与Pt-1的合成路线相同，唯一区别是，化合物11代替化合物2，化合物12代替化合物4，化合物10代替化合物6。化合物11的分子式如下所示：
Figure PCTCN2020116336-appb-000014
下面是本发明化合物的应用实例。
ITO/TAPC(70nm)/TCTA:Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(90nm)
器件制备方式：
依次使用丙酮、乙醇和蒸馏水对透明阳极氧化铟锡(ITO)(10Ω/sq)玻璃基板进行超声清洗,再用氧气等离子处理5分钟。
然后将ITO衬底安装在真空气相蒸镀设备的衬底固定器上。在蒸镀设备中，控制体系压力在10 -6torr.。
此后，向ITO衬底上蒸发厚度为70nm的空穴传输层(HTL)材料TAPC。
然后蒸发厚度为40nm的发光层材料(EML)TCTA，其中掺杂10％质量分数的铂(II)配合物。
然后蒸发厚度为30nm的电子传输层(ETL)材料TmPyPb。
然后蒸发厚度为1nm的LiF为电子注入层(EIL)。
最后蒸发厚度为90nm的Al作为阴极并完成器件封装。见图1所示。
Figure PCTCN2020116336-appb-000015
依次制备器件STD、器件1、器件2、器件3、器件4,器件的结构和制作方法完全相同，区别在于依次使用铂(II)配合物STD、Pt-1、Pt-2、Pt-3、Pt-12作为发光层中的掺杂剂。其中，参比材料STD为经典的具有ONCN配位结构的绿光材料。
Figure PCTCN2020116336-appb-000016
器件对比结果如表1所示，以器件STD的性能为基准；-表示数据持平，--表示相对基准性能降低了5％以上，+表示相对基准性能提升了5％，++表示相对基准性能提升了10％
  器件1 器件2 器件3 器件4
最大外量子效率 + + ++ ++
100nit下的外量子效率 + + + ++
启亮电压 -- - - -
100nit下的电流效率 + + + ++
由上表所示，基于本发明铂(II)配合物所制备的有机电致发光器件的性能相对于基准器件具有不同程度的性能提升。这类新型Pt(II)配合物分子立体性强，分子间的相互作用弱，避免了配合物分子之间互相堆叠，极大抑制了激基缔合物的形成，从而提高OLED器件的效率。综上所述，本发明所制备的有机电致发光器件的性能相对于基准器件具有较好的性能提升，所涉及的新型四齿铂(II)配合物金属有机材料具有较大的应用价值。

Claims (12)

  1. 一种四齿铂(II)配合物，具有如下式所示的结构：
    Figure PCTCN2020116336-appb-100001
    其中R 1－R 21独立的选自氢、氘、硫、卤素、羟基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲酰基、苄基羰基、芳氧基、二芳胺基、含1－30个C原子的饱和烷基、含2－20个C原子的不饱和烷基、取代的或未取代的含5－30个C原子的芳基、取代的或未取代的含5－30个C原子的杂芳基、或者相邻R 1－R 21相互通过共价键连接成环，其中取代为被卤素，氘、C1-C20烷基、C1-C10硅烷基、氰基取代，所述杂芳基中杂原子为N、O、S中的一个或多个。
  2. 根据权利要求1所述的配合物，其中R 1－R 21独立的选自氢、卤素、氨基、硝基、氰基、二芳胺基、含1－10个C原子的饱和烷基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的芳基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的杂芳基、或者相邻R 1－R 21相互通过共价键连接成环,所述卤素为F，Cl，Br。
  3. 根据权利要求2所述的配合物，其中R 1－R 21的21个基团中，其中有0－3个基团独立的表示为二芳胺基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的芳基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的含N杂芳基；其它的基团独立的表示为氢或含1－8个C原子的饱和烷基,所述卤素为F，Cl。
  4. 根据权利要求3所述的配合物，其中所述R 1－R 21的21个基团中，其中有0－3个基团独立的表示为二苯胺基、苯基、吡啶基、咔唑基，其它基团独立的表示为氢、氟或者1－4个C原子的饱和烷基。
  5. 根据权利要求1所述的配合物，具有如下式所示的结构：
    Figure PCTCN2020116336-appb-100002
    其中R 1’－R 6’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、被卤素或一个或多个C1－C4烷基取代的或未取代的含5－20个C原子的芳基、被卤素或一个或多个 C1－C4烷基取代的或未取代杂的含5－20个C原子的芳基、或者相邻R 1’－R 6’相互通过共价键连接成环，所述卤素为F，Cl，Br，所述杂芳基中杂原子为N、O、S中的任一一种。
  6. 根据权利要求5所述的配合物，其中R 1’－R 6’的6个基团中，其中有0－3个基团独立的表示为二芳胺基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的芳基、被卤素或1至3个C1－C4烷基取代的或未取代的含5－10个C原子的杂芳基；其它的基团独立的表示为氢、卤素或含1－8个C原子的饱和烷基，所述卤素为F，Cl。
  7. 根据权利要求1所述的配合物，其中R 1’－R 6’的6个基团中，其中有0－3个基团独立的表示为二苯胺基、C1-C4烷基取代或未取代的苯基、吡啶基、咔唑基，其它基团独立的表示为氢、氟、含1－4个C原子的饱和烷基。
  8. 根据权利要求1所述的配合物，具有如下结构：
    Figure PCTCN2020116336-appb-100003
    Figure PCTCN2020116336-appb-100004
    Figure PCTCN2020116336-appb-100005
  9. 权利要求1-8任一所述的配合物的前体，即配体，其结构式如下：
    Figure PCTCN2020116336-appb-100006
    其中R 1－R 21独立的选自氢、氘、硫、卤素、羟基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲酰基、苄基羰基、芳氧基、二芳胺基、含1－30个C原子的饱和烷基、含2－20个C原子的不饱和烷基、取代的或未取代的含5－ 30个C原子的芳基、取代的或未取代的含5－30个C原子的杂芳基、或者相邻R 1－R 21相互通过共价键连接成环，其中取代为被卤素，氘、C1-C20烷基、C1-C10硅烷基、氰基取代，所述杂芳基中杂原子为N、O、S中的一个或多个。
  10. 根据权利要求5所述的四齿铂(II)配合物的合成方法，包括如下步骤：
    初始底物S1与S2经Suzuki-Miyaura偶联反应得到底物S3，S3与S4经Buchwald–Hartwig偶联反应得到底物S5，S5与S6经Buchwald–Hartwig偶联反应得到底物S7,S7在吡啶盐酸盐作用下高温加热脱甲基得到S8，S8与K 2PtCl 4螯合反应即得到目标铂(II)配合物TM，
    Figure PCTCN2020116336-appb-100007
  11. 权利要求1－8任一所述配合物在OLED发光器件中的应用。
  12. 根据权利要求9所述的应用，所述权利要求1－8任一所述配合物为发光层中起光子发射作用的磷光掺杂材料。
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