WO2020134569A1 - 一种n^n^c^o型四齿铂(ii)配合物的制备及应用 - Google Patents

一种n^n^c^o型四齿铂(ii)配合物的制备及应用 Download PDF

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WO2020134569A1
WO2020134569A1 PCT/CN2019/115181 CN2019115181W WO2020134569A1 WO 2020134569 A1 WO2020134569 A1 WO 2020134569A1 CN 2019115181 W CN2019115181 W CN 2019115181W WO 2020134569 A1 WO2020134569 A1 WO 2020134569A1
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atoms
halogen
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substituted
alkyl
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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 US17/298,002 priority Critical patent/US20220115605A1/en
Priority to KR1020217013133A priority patent/KR102646935B1/ko
Priority to JP2021529326A priority patent/JP7195668B2/ja
Priority to DE112019005247.0T priority patent/DE112019005247B4/de
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to a novel N ⁇ N ⁇ C ⁇ O tetradentate platinum (II) complex metal organic material, especially a phosphorescent doping material used for photon emission in the light emitting layer of an OLED light emitting device.
  • II tetradentate platinum
  • OLED Organic Light-Emitting Diode
  • Platinum (II) is generally a four-coordinated site, and a metal-organic platinum (II) complex with a unique configuration can be formed by designing a tetradentate ligand.
  • platinum (II) complexes are relatively slow, especially for the development of new platinum (II) complex phosphorescent luminescent materials, for the promotion of platinum ( II)
  • the commercial application of the complex is particularly important. Summary of the invention
  • novel N ⁇ N ⁇ C ⁇ O tetradentate platinum(II) complex metal organic material involved in the present invention has the structure shown in the following figure:
  • R 1 -R 15 are independently selected from hydrogen, deuterium, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carbamoyl, benzylcarbonyl, aryloxy, diarylamino, saturated alkyl containing 1-30 C atoms, unsaturated alkyl containing 1-20 C atoms, substituted with 5-30 C atoms Substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups containing 5 to 30 C atoms, or adjacent R 1 to R 15 are connected to each other through a covalent bond to form a ring.
  • R 1 -R 15 are independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl containing 1-10 C atoms, coatings containing 5-20 C atoms Halogen or one or more C1-C4 alkyl substituted or unsubstituted aryl groups, containing 5 to 20 C atoms, halogen or one or more C1-C4 alkyl substituted or unsubstituted heteroaryl groups, or phase
  • the ortho-R 1 -R 15 are connected to each other through a covalent bond to form a ring, and the halogen is F, Cl, Br.
  • R 1 -R 15 0-3 of which are independently represented as diarylamine groups, contain 5-10 C atoms by halogen or 1 to 3 C1-C4 alkanes
  • 0 to 3 groups are independently represented as diphenylamino, phenyl, pyridyl, and carbazolyl, and other groups are independently represented as Hydrogen, fluorine or saturated alkyl group with 1 to 4 C atoms.
  • R 1 '-R 5' are independently selected from hydrogen, halogen, di-arylamino, saturated alkyl group containing 1-10 C atoms, containing 5 to 20 C atoms or one or more halogen C1- C4 alkyl substituted or unsubstituted aryl group containing 5-20 C atoms or by one or more halogen, C1-C4 alkyl substituted or unsubstituted heteroaryl or adjacent R 1 '-R 5' Connected to each other through a covalent bond to form a ring, the halogen is F, Cl, Br.
  • R 1 ′-R 5 ′ are independently represented as diarylamine groups, containing 5-10 C atoms by halogen or 1 to 3 C1- C4 alkyl substituted or unsubstituted aryl, 5-10 C atoms substituted by halogen or 1 to 3 C1-C4 alkyl substituted or unsubstituted heteroaryl; other groups are independently expressed as Hydrogen, halogen or saturated alkyl group containing 1-8 C atoms, the halogen is F, Cl.
  • R 1 ′-R 5 ′ among which 0-3 groups are independently represented as diphenylamino, C1-C4 alkyl substituted or unsubstituted phenyl, pyridyl, carbazine Zazolyl, other groups are independently represented as hydrogen, fluorine, saturated alkyl containing 1-4 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, most preferably F.
  • ring, aryl, and heteroaryl groups connected by a covalent bond include 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and are fused by one aromatic ring or multiple Aryl group consisting of aromatic rings.
  • Suitable aryl groups are, for example, phenyl, naphthyl, acenaphthenyl, acenaphthenyl, anthracenyl, fluorenyl, phenalenyl.
  • the aryl group may be unsubstituted (ie, 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, preferably alkyl having 1-20, 1-10 or 1-8 carbon atoms, particularly preferably methyl, ethyl, isopropyl Group or tert-butyl group; aryl group, preferably re-substituted or unsubstituted C 5 , C 6 aryl group or fluorenyl group; heteroaryl group, preferably a heteroaryl group containing at least one nitrogen atom, particularly preferably pyridyl;
  • the aryl group particularly particularly preferably carries a substituent selected from F and tert-butyl, preferably an aryl group which may be a given aryl group or optionally substituted by
  • the unsaturated alkyl group having 1 to 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 to 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 regarding aryl groups.
  • alkyl groups it is possible to carry one or more aryl groups, all of which are suitable for this purpose, 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 connected to the CO group with a single bond, such as an alkyl group as used herein.
  • alkoxy group is directly connected to oxygen by a single bond, as used herein an alkyl group.
  • the above heteroaryl group is understood to be related to an aromatic, C 3 -C 8 ring group, and also contains an oxygen or sulfur atom or 1-4 nitrogen atoms or a combination of an oxygen or sulfur atom and up to two nitrogen atoms , And their substituted and benzo and pyrido fused derivatives, for example, through one of the ring-forming carbon atoms, the heteroaryl group may be substituted by one or more of the substituents mentioned for aryl Replaced by.
  • the heteroaryl group may be a five- or six-membered aromatic heterocyclic ring system carrying the above independent groups containing 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, benzisoazole, 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, pyridine, benzoxazole, diazole,
  • 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. Specific examples shown below include but are not limited to the following structures:
  • the precursor of the above complex that is, the ligand, has the structural formula as follows:
  • R 1- R 15 are independently selected from hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl containing 1-10 C atoms, halogenated containing 5-20 C atoms or One or more C1-C4 alkyl-substituted or unsubstituted aryl groups, containing 5 to 20 C atoms, halogen-substituted or one or more C1-C4 alkyl-substituted or unsubstituted heteroaryl groups, or adjacent R 1- R 15 are connected to each other through a covalent bond to form a ring.
  • R 1 '-R 5' are independently selected from hydrogen, halogen, di-arylamino, saturated alkyl group containing 1-10 C atoms, containing 5 to 20 C atoms or one or more halogen C1- C4 alkyl substituted or unsubstituted aryl group containing 5-20 C atoms or by one or more halogen, C1-C4 alkyl substituted or unsubstituted heteroaryl or adjacent R 1 '-R 5' Connected to each other through a covalent bond to form a ring, the halogen is F, Cl, Br.
  • an OLED device of thermal deposition and solution treatment can be manufactured.
  • the complex is applied as 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 device emits orange-red when current is applied.
  • the organic metal complex in the present invention has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can produce orange-red light OLED devices with high luminous efficiency and low roll-off.
  • FIG. 1 is a schematic structural diagram of an organic electroluminescent device of the present invention.
  • the preparation method of the above complex includes the following steps:
  • the initial substrates S1 and S2 are subjected to Buchwald–Hartwig coupling reaction to obtain substrate S3, and S3 and S4 are subjected to Buchwald–Hartwig coupling reaction to obtain substrate S5, and S5 is demethylated under the action of pyridine hydrochloride to obtain S6.
  • S6 reacts with K 2 PtCl 4 to obtain the target product P.
  • Synthesis of compound 8 take compound 7 27.53g (0.10mol), compound 2 26.92g (0.10mol), palladium acetate 450mg (0.02eq., 2mmol), triphenylphosphine 1.05g (0.04eq., 4mmol), tertiary 22.44 g (2.0 eq., 0.20 mol) of potassium butoxide was added to the flask, 250 mL of dioxane was added, and the mixture was heated and refluxed under nitrogen for 8 hours.
  • Synthesis of compound 10 take compound 8 23.18g (50mmol), compound 9 14.56g (50mmol), palladium acetate 225mg (0.02eq., 1mmol), triphenylphosphine 0.53g (0.04eq., 2mmol), tert-butanol Potassium 11.22g (2.0eq., 0.10mol) was added to the flask, 200mL of dioxane was added, and the mixture was heated and refluxed under nitrogen for 8 hours.
  • Synthesis of compound 13 Take compound 1 19.92g (0.10mol), compound 12 24.12g (0.10mol), palladium acetate 450mg (0.02eq., 2mmol), triphenylphosphine 1.05g (0.04eq., 4mmol), tertiary 22.44 g (2.0 eq., 0.20 mol) of potassium butoxide was added to the flask, 250 mL of dioxane was added, and the mixture was heated and refluxed under nitrogen for 8 hours.
  • Synthesis of compound 18 take compound 17 30.34g (0.10mol), compound 2 26.92g (0.10mol), palladium acetate 450mg (0.02eq., 2mmol), triphenylphosphine 1.05g (0.04eq., 4mmol), tertiary 22.44 g (2.0 eq., 0.20 mol) of potassium butoxide was added to the flask, 300 mL of dioxane was added, and the mixture was heated at reflux under nitrogen for 8 hours.
  • Synthesis of compound 20 take compound 18 25.58g (50mmol), compound 19 16.96g (50mmol), palladium acetate 225mg (0.02eq., 1mmol), triphenylphosphine 0.53g (0.04eq., 2mmol), tert-butanol Potassium 11.22g (2.0eq., 0.10mol) was added to the flask, 300mL of dioxane was added, and the reaction was heated at reflux under nitrogen for 8 hours.
  • ITO/TAPC(60nm)/TCTA Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(80nm)
  • the transparent anodized tin indium tin oxide (ITO, 20) (10 ⁇ /sq) glass substrate 10 was ultrasonically cleaned using acetone, ethanol and distilled water in sequence, and then treated with oxygen plasma for 5 minutes.
  • the ITO substrate is mounted on the substrate holder of the vacuum vapor deposition equipment.
  • control the system pressure at 10 -6 torr.
  • the hole transport layer (30) material TAPC with a thickness of 60 nm is evaporated onto the ITO substrate.
  • the luminescence layer material (40) TCTA with a thickness of 40 nm is evaporated, in which platinum (II) complex dopants of different mass fractions are doped.
  • the electron transport layer (50) material TmPyPb with a thickness of 30 nm is then evaporated.
  • LiF with a thickness of 1 nm is evaporated as an electron injection layer (60).
  • the structure and manufacturing method of the device are exactly the same, the difference is that the organometallic complexes P0, P1, P6, P24, and P45 are used sequentially as the dopant and doping concentration in the light-emitting layer.
  • Pt0 is a classic O ⁇ N ⁇ N ⁇ O type red light material.
  • the doping concentration of the tetradentate platinum(II) complex is 4wt%, 8wt% and 12wt%
  • the above ITO/HTL-1(60nm)/EML-1:Pt(II)(40nm)/ETL- 1(30nm)/LiF(1nm)/Al(80nm) device basic structure to prepare the device.
  • the start-up voltage V on of the four-tooth platinum (II) complexes P1, P6, P24, and P45 devices is reduced to varying degrees compared to Pt0 devices.
  • the current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) of the devices based on P1, P6, P24, P45 have different degrees compared to the devices based on Pt-0.
  • the improvement, especially P45, is more obvious in current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE).
  • the doping concentration of the tetradentate platinum (II) complex increases, the efficiency of P1, P6, P24, and P45 are improved to varying degrees.
  • P45 has a larger steric hindrance group, which can effectively reduce the aggregation between molecules, avoid the formation of exciplex, and improve the luminous efficiency.
  • the central platinum (II) is a six-membered ring + six-membered ring + five-membered ring chelating coordination mode
  • the formed complex is stable
  • the rigid structure is strong
  • the energy Reducing the dissipation of non-radiative energy such as intramolecular rotation and vibration is conducive to the improvement of the luminous efficiency and performance of the platinum(II) complex.
  • the triphenylamine structure in the ligand skeleton can be easily added with different substituents to facilitate the optimization and regulation of molecular structure.
  • the performance of the organic electroluminescent device prepared by the present invention is better than that of the reference device, and the new N ⁇ N ⁇ C ⁇ O tetradentate platinum (II) complex metal organic material is involved Has greater application value.

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Abstract

下式所示的N^N^C^O型四齿铂（II）配合物及其配体、制备方法和应用。所述配合物用于OLED发光器件的发光层中起光子发射作用的磷光掺杂材料。

Description

一种N^N^C^O型四齿铂(II)配合物的制备及应用 技术领域
本发明涉及一种新型的N^N^C^O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)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。
在OLED材料领域，磷光类OLED发光层掺杂材料发展较为迅速与成熟，其主要是基于一些重金属有机配合物，如铱、铂、铕、锇等。磷光材料在发光过程中可以充分利用单线态和三线态激子的能量，因此理论上其量子效率可达到100％，是目前业界使用比较广的发光材料。
其中，近些年来基于铂(II)的磷光OLED材料表现出了较好的显示性能。铂(II)一般为四配位点，可以通过设计四齿配体形成具有唯一构型的金属有机铂(II)配合物。但是相对于应用成熟的铱(III)配合物发光材料，铂(II)配合物的开发与应用相对较为迟缓，尤其是对于新型的铂(II)配合物磷光发光材料的开发，对于推进铂(II)配合物的商业化应用显得尤为重要。发明内容
本发明所涉及的新型的N^N^C^O四齿铂(II)配合物金属有机材料，具有如下图所示的结构：
Figure PCTCN2019115181-appb-000001
其中R 1－R 15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1－20个C原子的不饱和烷基、含5－30个C原子取代的或未取代的芳基、含5－30个C原子取代的或未取代的杂芳基、或者相邻R 1－R 15相互通过共价键连接成环。
优选：其中R 1－R 15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、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1－R 15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 15的15个基团中，其中有0－3个基团独立的表示为二芳胺基、含5－10个C原子被卤素或1至3个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或1至3个C1－C4烷基取代的或未取代的含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 15的15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 PCTCN2019115181-appb-000002
其中R 1’－R 5’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1’－R 5’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 5’的5个基团中，其中有0－3个基团独立的表示为二芳胺基、含5－10个C原子被卤素或1至3个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或1至3个C1－C4烷基取代的或未取代的杂芳基；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 5’的5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。
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和叔丁基的取代基，优选可为给定的芳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 PCTCN2019115181-appb-000003
Figure PCTCN2019115181-appb-000004
Figure PCTCN2019115181-appb-000005
Figure PCTCN2019115181-appb-000006
Figure PCTCN2019115181-appb-000007
上述配合物的前体，即配体，其结构式如下：
Figure PCTCN2019115181-appb-000008
其中R 1－R 15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、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1－R 15相互通过共价键连接成环。
优选：
Figure PCTCN2019115181-appb-000009
其中R 1’－R 5’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1’－R 5’相互通过共价键连接成环，所述卤素为F，Cl，Br。
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Buchwald–Hartwig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在吡啶盐酸盐作用下脱甲基得到S6，S6与K 2PtCl 4反应即得到目标产物P。
Figure PCTCN2019115181-appb-000010
本发明中化合物合成中涉及的初始底物和溶剂均购自安耐吉，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 PCTCN2019115181-appb-000011
Figure PCTCN2019115181-appb-000012
化合物3的合成：取化合物1 19.92g(0.10mol)，化合物2 26.92g(0.10mol)，醋酸钯450mg(0.02eq.,2mmol)，三苯基膦1.05g(0.04eq.,4mmol)，叔丁醇钾22.44g(2.0eq.,0.20mol)于烧瓶中，加入200mL二氧六环，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甲醇重结晶得到目标产物化合物3 32.18g，产率90％，纯度99.5％。
化合物5的合成：取化合物3 17.88g(50mmol)，化合物4 11.75g(50mmol)，醋酸钯225mg(0.02eq.,1mmol)，三苯基膦0.53g(0.04eq.,2mmol)，叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中，加入200mL二氧六环，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甲醇重结晶得到目标产物化合物5 23.83g，产率88％，纯度99.9％。
化合物6的合成：取化合物5 5.42g(10mmol)，吡啶盐酸盐30g，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甲醇重结晶得到目标产物化合物6 4.48g，产率85％，纯度99.9％。质谱(ESI -)([M-H] -)C 36H 37N 3O理论值:526.29；实测值:526.26。
化合物P1的合成：取1.06g(2.0mmol)化合物6,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol)，溶于25mL乙酸中，抽真空通入氮气置换数次，搅拌加热至130℃反应12hr。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，使用正己烷/乙酸乙酯体系柱层析，将得到的粗品真空升华得到红色固体648mg，总产率45％，纯度99.9％。质谱(ESI -)([M-H] -)C 36H 34N 3OPt理论值:719.24；实测值:719.23。
实施例2：
Figure PCTCN2019115181-appb-000013
Figure PCTCN2019115181-appb-000014
化合物8的合成：取化合物7 27.53g(0.10mol)，化合物2 26.92g(0.10mol)，醋酸钯450mg(0.02eq.,2mmol)，三苯基膦1.05g(0.04eq.,4mmol)，叔丁醇钾22.44g(2.0eq.,0.20mol)于烧瓶中，加入250mL二氧六环，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甲醇重结晶得到目标产物化合物8 40.82g，产率88％，纯度99.5％。
化合物10的合成：取化合物8 23.18g(50mmol)，化合物9 14.56g(50mmol)，醋酸钯225mg(0.02eq.,1mmol)，三苯基膦0.53g(0.04eq.,2mmol)，叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中，加入200mL二氧六环，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甲醇重结晶得到目标产物化合物10 30.32g，产率90％，纯度99.9％。
化合物11的合成：取化合物10 6.74g(10mmol)，吡啶盐酸盐40g，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甲醇重结晶得到目标产物化合物11 5.28g，产率80％，纯度99.9％。质谱(ESI -)([M-H] -)C 46H 48N 3O理论值:658.39；实测值:658.37。
化合物P6的合成：取1.32g(2.0mmol)化合物6,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol)，溶于25mL乙酸中，抽真空通入氮气置换数次，搅拌加热至130℃反应12hr。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，使用正己烷/乙酸乙酯体系柱层析，将得到的粗品真空升华得到红色固体716mg，总产率42％，纯度99.9％。质谱(ESI -)([M-H] -)C 46H 46N 3OPt理论值:851.34；实测值:851.32。
实施例3：
Figure PCTCN2019115181-appb-000015
Figure PCTCN2019115181-appb-000016
化合物13的合成：取化合物1 19.92g(0.10mol)，化合物12 24.12g(0.10mol)，醋酸钯450mg(0.02eq.,2mmol)，三苯基膦1.05g(0.04eq.,4mmol)，叔丁醇钾22.44g(2.0eq.,0.20mol)于烧瓶中，加入250mL二氧六环，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甲醇重结晶得到目标产物化合物13 32.36g，产率90％，纯度99.5％。
化合物15的合成：取化合物13 17.98g(50mmol)，化合物14 19.78g(50mmol)，醋酸钯225mg(0.02eq.,1mmol)，三苯基膦0.53g(0.04eq.,2mmol)，叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中，加入250mL二氧六环，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甲醇重结晶得到目标产物化合物15 28.64g，产率85％，纯度99.9％。
化合物16的合成：取化合物15 6.74g(10mmol)，吡啶盐酸盐40g，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甲醇重结晶得到目标产物化合物16 5.61g，产率85％，纯度99.9％。质谱 (ESI -)([M-H] -)C 46H 48N 3O理论值:658.39；实测值:658.37。
化合物P24的合成：取1.32g(2.0mmol)化合物16,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol)，溶于25mL乙酸中，抽真空通入氮气置换数次，搅拌加热至130℃反应12hr。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，使用正己烷/乙酸乙酯体系柱层析，将得到的粗品真空升华得到红色固体682mg，总产率40％，纯度99.9％。质谱(ESI -)([M-H] -)C 46H 46N 3OPt理论值:851.34；实测值:851.32。
实施例4：
Figure PCTCN2019115181-appb-000017
Figure PCTCN2019115181-appb-000018
化合物18的合成：取化合物17 30.34g(0.10mol)，化合物2 26.92g(0.10mol)，醋酸钯450mg(0.02eq.,2mmol)，三苯基膦1.05g(0.04eq.,4mmol)，叔丁醇钾22.44g(2.0eq.,0.20mol)于烧瓶中，加入300mL二氧六环，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甲醇重结晶得到目标产物化合物18 44.25g，产率90％，纯度99.5％。
化合物20的合成：取化合物18 25.58g(50mmol)，化合物19 16.96g(50mmol)，醋酸钯225mg(0.02eq.,1mmol)，三苯基膦0.53g(0.04eq.,2mmol)，叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中，加入300mL二氧六环，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甲醇重结晶得到目标产物化合物20 30.75g，产率82％，纯度99.9％。
化合物21的合成：取化合物20 7.50g(10mmol)，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甲醇重结晶得到目标产物化合物21 5.89g，产率80％，纯度99.9％。质谱(ESI -)([M-H] -)C 52H 52N 3O理论值:734.42；实测值:734.40。
化合物P45的合成：取1.47g(2.0mmol)化合物21,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol)，溶于25mL乙酸中，抽真空通入氮气置换数次，搅拌加热至130℃反应12hr。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，使用正己烷/乙酸乙酯体系柱层析，将得到的粗品真空升华得到红色固体780mg，总产率42％，纯度99.9％。质谱(ESI -)([M-H] -)C 50H 50N 3OPt理论值:927.37；实测值:927.35。
对于实施例的Pt(II)配合物，在二氯甲烷溶液溶液中呈现出明显的橙红光发射。如下表所示：
Figure PCTCN2019115181-appb-000019
Figure PCTCN2019115181-appb-000020
Figure PCTCN2019115181-appb-000021
下面是本发明化合物的应用实例。
ITO/TAPC(60nm)/TCTA:Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(80nm)
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,20)(10Ω/sq)玻璃基板10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60nm的空穴传输层(30)材料TAPC。
然后蒸发厚度为40nm的发光层材料(40)TCTA，其中掺杂不同质量分数的铂(II)配合物掺杂剂。
然后蒸发厚度为30nm的电子传输层(50)材料TmPyPb。
然后蒸发厚度为1nm的LiF为电子注入层(60)。
最后蒸发厚度为80nm的Al作为阴极(70)并完成器件封装。见图1所示。
Figure PCTCN2019115181-appb-000022
器件的结构和制作方法完全相同，区别在于依次使用有机金属配合物P0、P1、P6、P24、P45作为发光层中的掺杂剂与掺杂浓度。其中，Pt0为经典的O^N^N^O类红光材料。
Figure PCTCN2019115181-appb-000023
器件对比结果下表所示：
Figure PCTCN2019115181-appb-000024
在四齿铂(II)配合物掺杂浓度分别为4wt％，8wt％，12wt％条件下，以上述ITO/HTL-1(60nm)/EML-1:Pt(II)(40nm)/ETL-1(30nm)/LiF(1nm)/Al(80nm)器件基本结构制备器件。以基于Pt0的器件性能为参考，四齿铂(II)配合物P1、P6、P24、P45的器件在启动电压V on相比Pt0的器件均有不同程度的降低。同时，在1000cd/A条件下，基于P1、P6、P24、P45的器件在电流效率(CE)，功率效率(PE)和外量子效率(EQE)相对于基于Pt-0的器件均有不同程度的提升，尤其是P45,在电流效率(CE)，功率效率(PE)和外量子效率(EQE)上提升较为明显。在四齿铂(II)配合物掺杂浓度增加时，P1、P6、P24、P45的效率均有不同程度的提升。P45相对于P1、P6、P24有较大的位阻基团，能有效降低分子间的聚集作用，避免形成激基复合物，提高发光效率。
本发明所涉及的四齿铂(II)配合物，中心铂(II)为六元环+六元环+五元环螯合配位方式，形成的配合物稳定，刚性结构强，能较大减少分子内旋转和振动等非辐射能量耗散，有利于 铂(II)配合物发光效率与性能的提高。同时，配体骨架中的三苯胺结构部分，可以较为容易的添加不同的取代基，方便实现分子结构的优化与调控。
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N^N^C^O四齿铂(II)配合物金属有机材料具有较大的应用价值。

Claims (14)

  1. 一种N^N^C^O四齿铂(II)配合物，具有如下式所示的结构：
    Figure PCTCN2019115181-appb-100001
    其中R 1－R 15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1－20个C原子的不饱和烷基、含5－30个C原子取代的或未取代的芳基、含5－30个C原子取代的或未取代的杂芳基、或者相邻R 1－R 15相互通过共价键连接成环。
  2. 根据权利要求1所述的配合物，其中R 1－R 15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、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1－R 15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 15的15个基团中，其中有0－3个基团独立的表示为二芳胺基、含5－10个C原子被卤素或1至3个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或1至3个C1－C4烷基取代的或未取代的含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 15的15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2所述的配合物，具有如下式所示的结构：
    Figure PCTCN2019115181-appb-100002
    其中R 1’－R 5’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、含5－20 个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1’－R 5’相互通过共价键连接成环，所述卤素为F，Cl，Br。
  6. 根据权利要求5所述的配合物，其中R 1’－R 5’的5个基团中，其中有0－3个基团独立的表示为二芳胺基、含5－10个C原子被卤素或1至3个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或1至3个C1－C4烷基取代的或未取代的杂芳基；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6所述的配合物，其中R 1’－R 5’的5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 PCTCN2019115181-appb-100003
    Figure PCTCN2019115181-appb-100004
    Figure PCTCN2019115181-appb-100005
    Figure PCTCN2019115181-appb-100006
    Figure PCTCN2019115181-appb-100007
  9. 根据权利要求8所述的配合物，其具有如下结构：
    Figure PCTCN2019115181-appb-100008
    Figure PCTCN2019115181-appb-100009
  10. 权利要求1-9任一所述的配合物的前体，即配体，其结构式如下：
    Figure PCTCN2019115181-appb-100010
    其中R 1－R 15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、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1－R 15相互通过共价键连接成环。
  11. 根据权利要求10所述的前体，其结构式如下：
    Figure PCTCN2019115181-appb-100011
    其中R 1’－R 5’独立的选自氢、卤素、二芳胺基、含1－10个C原子的饱和烷基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代芳基、含5－20个C原子的被卤素或一个或多个C1－C4烷基取代的或未取代杂芳基、或者相邻R 1’－R 5’相互通过共价键连接成环，所述卤素为F，Cl，Br。
  12. 根据权利要求1-9任一所述的N^N^C^O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Buchwald–Hartwig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在吡啶盐酸盐作用下脱甲基得到S6，S6与K 2PtCl 4反应即得到目标产物P，反应式如下：
    Figure PCTCN2019115181-appb-100012
  13. 权利要求1－9任一所述配合物在OLED发光器件中的应用。
  14. 根据权利要求13所述的应用，所述权利要求1－9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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