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WO2019128895A1 - Tetradentate platinum (ii) complex material based on oxazole, thiazole or imidazole and use - Google Patents

Tetradentate platinum (ii) complex material based on oxazole, thiazole or imidazole and use Download PDF

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WO2019128895A1
WO2019128895A1 PCT/CN2018/122965 CN2018122965W WO2019128895A1 WO 2019128895 A1 WO2019128895 A1 WO 2019128895A1 CN 2018122965 W CN2018122965 W CN 2018122965W WO 2019128895 A1 WO2019128895 A1 WO 2019128895A1
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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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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Definitions

  • the invention relates to a novel tetradentate platinum (II) complex metal organic material based on oxazole, thiazole and imidazole, which is mainly used in an OLED light-emitting device as a phosphorescent dopant material in a light-emitting layer.
  • II tetradentate platinum
  • OLED Organic Light-Emitting Diode
  • OLED display technology has the advantages of self-luminous, wide viewing angle, almost infinite contrast, low power consumption, high reaction speed, etc.
  • OLED has potential flexible folding characteristics, and thus has been widely concerned and studied, but OLED
  • the shortcomings of short service life, poor color purity, and aging are hindering the large-scale application of OLED technology. Therefore, designing new OLED materials is the focus and difficulty of OLED research.
  • platinum (II)-based phosphorescent OLED materials have shown good display performance in recent years.
  • Platinum (II) is generally a tetracoordinated site, and a metal organoplatinum (II) complex having a unique configuration can be formed by designing a tetradentate ligand.
  • the common tetradentate ligands are mainly O ⁇ N ⁇ N ⁇ O, O ⁇ N ⁇ C ⁇ O, O ⁇ N ⁇ C ⁇ N and the like.
  • O ⁇ N ⁇ N ⁇ O tetradentate platinum (II) complexes are mainly Schiff bases, which are relatively common, but the stability is relatively poor; O ⁇ N ⁇ C ⁇ O four teeth Platinum (II) complexes are relatively stable, but performance needs to be improved.
  • the designed and synthesized N ⁇ N ⁇ N ⁇ O configuration tetradentate platinum (II) complex is a novel coordination mode, showing good stability and luminescence properties.
  • O ⁇ N ⁇ N ⁇ O tetradentate platinum (II) complexes are mainly Schiff bases, which are relatively common, but the stability is relatively poor; O ⁇ N ⁇ C ⁇ O and O ⁇ The N ⁇ C ⁇ N tetradentate platinum (II) complex is relatively stable, but its performance needs to be improved.
  • the general O ⁇ N ⁇ C ⁇ N configuration of tetradentate platinum (II) complexes the structure of which is mainly composed of six-membered aromatic ring ligands.
  • a novel tetradentate platinum (II) complex based on a five-membered aromatic ring derivative oxazole, thiazole and imidazole is designed and synthesized, and exhibits good stability and luminescence properties.
  • the invention designs a novel O ⁇ N ⁇ C ⁇ N tetradentate platinum (II) complex material based on oxazole, thiazole and imidazole, and can be applied as a phosphorescent dopant material in the field of OLED.
  • the organometallic complex has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can manufacture a yellow-green light OLED device with high efficiency and low efficiency roll-off.
  • the invention also provides a preparation method of the novel platinum (II) complex.
  • a 1 -A 4 is a substituted or unsubstituted five-membered ring, six-membered ring, fused ring structure;
  • X is oxygen, sulfur or substituted nitrogen (-NR 0 ), and R 0 is substituted by one or more R Or unsubstituted C1-C8 alkyl, C5-C20 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamino, oxazolyl, fluorenyl.
  • the structure may preferably be a structure as shown in the formula (2):
  • R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen-NR 0 , R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroary
  • R 1 to R 14 are independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl having 1 to 10 C atoms, and having 5 to 20 C atoms Halogen or one or more C1-C4 alkyl-substituted or unsubstituted aryl groups, 5-20 C atoms substituted by halogen or one or more C1-C4 alkyl groups or unsubstituted heteroaryl groups, or phases
  • the adjacent R 1 -R 14 are bonded to each other by a covalent bond, X is oxygen, sulfur or substituted nitrogen -NR 0 , and R 0 is the following substituent:
  • R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
  • R' 1 to R' 4 0-3 of the groups are independently represented by a diarylamine group
  • 5-10 C atoms are halogenated or one to three C1-C4 alkane a substituted or unsubstituted aryl group, a halogen-containing or one to three C1-C4 alkyl-substituted or unsubstituted heteroaryl group having 5 to 10 C atoms
  • the other groups are independently represented as hydrogen or A saturated alkyl group of 1 to 6 C atoms.
  • one of R' 2 to R' 4 is selected from the group consisting of diphenylamine, benzene, pyridine, carbazolyl, isopropyl or tert-butyl, and the other groups are independently represented by hydrogen; R' 1 represents It is hydrogen.
  • R' 1 to R' 4 are represented by hydrogen; X is oxygen, sulfur or substituted nitrogen -NR 0 , and R 0 is a C1-C8 alkyl group.
  • X is O, S, NR 0 , including but not limited to the following structure:
  • the precursor of the above complex ie, the ligand, has the following structural formula:
  • a 1 -A 4 is a substituted or unsubstituted five-membered ring, a six-membered ring, a fused ring structure;
  • X is oxygen, sulfur or a substituted nitrogen (-NR 0 ), and R 0 is a substituent, and R 0 is One or more R substituted or unsubstituted C1-C8 alkyl, C5-C20 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamino, oxazolyl, fluorenyl.
  • R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen-NR 0 , R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroary
  • R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
  • o-phenylammonium B1 reacts with aromatic aldehyde B2 to obtain B3.
  • B3 reacts with halogenated compounds under basic conditions to obtain B4, and B4 further reacts to obtain the corresponding pinacol.
  • the ester B5, B5 and B6 are reacted by Suzuki to obtain the substrate B7, and the B7 is demethylated to obtain the ligand B8, and the B8 reacts with K 2 PtCl 4 to obtain the corresponding target product B.
  • halogen alkyl, cycloalkyl, aryl, acyl, alkoxy, and heterocyclic aromatic or heterocyclic aromatic groups may have the following meanings, unless otherwise indicated:
  • halogen or halogen includes fluorine, chlorine, bromine and iodine, preferably F, Cl, Br, particularly preferably F or Cl, most preferably F.
  • the above covalent bond is bonded to a ring, aryl, heteroaryl or fused ring structure comprising from 5 to 30 carbon atoms, preferably from 5 to 20 carbon atoms, more preferably from 5 to 10 carbon atoms and from one aromatic ring or more An aryl group consisting of a fused aromatic ring.
  • Suitable aryl groups are, for example, phenyl, naphthyl, acenaphthenyl, acenaphthenyl, fluorenyl, fluorenyl, phenalenyl.
  • the aryl group may be unsubstituted (i.e., all carbon atoms capable of substituting a hydrogen atom) 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 having from 1 to 20, from 1 to 10 or from 1 to 8 carbon atoms, particularly preferably methyl, ethyl or isopropyl Or a tert-butyl group; an aryl group, preferably a substituted or unsubstituted C 5 , C 6 aryl or anthracenyl group; the aryl group particularly preferably has a substituent selected from the group consisting of F and a t-butyl group, preferably a given aryl group or an aryl group which is a C 5 ,C 6 aryl group optionally substituted by at least one of the above substituents, and a C 5 ,
  • a heteroaryl group preferably a heteroaryl group containing at least one nitrogen atom, particularly preferably a pyridyl group
  • an unsaturated alkyl group is preferably an alkenyl group, preferably an alkenyl group having one double bond, particularly preferably having a double bond and 1-8 carbon atoms Alkenyl.
  • the above alkyl or alkyl moiety includes an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • the alkyl group may be branched or linear, or may be cyclic, and may be interrupted by one or more heteroatoms, preferably N, O or S.
  • the alkyl group may be substituted by one or more halogens or the above-mentioned substituents with respect to the aryl group.
  • the alkyl group may have one or more aryl groups, all of which are suitable for this purpose, the alkyl group being particularly preferred from methyl, ethyl, isopropyl, n-propyl, Isobutyl, n-butyl, tert-butyl, sec-butyl, isopentyl, cyclopropyl, cyclopentyl, cyclohexyl.
  • acyl group is an alkyl group which is bonded to a CO group by a single bond, as used herein.
  • the above alkoxy group is directly bonded to oxygen as a single bond, as used herein.
  • the above heteroaryl is understood to be related to an aryl group, a C 3 -C 8 ring group, and further comprises an oxygen or sulfur atom or a combination of 1 to 4 nitrogen atoms or an oxygen or sulfur atom and up to two nitrogen atoms, And their substituted and benzopyridinium-fused derivatives, for example, via one of the ring-forming carbon atoms, which may be referred to by one or more of the hetero-aromatic groups Substituted by an aryl group.
  • a heteroaryl group can be a five or six membered aromatic heterocyclic ring system containing the above independent zero, one or two substituents.
  • Typical examples of heteroaryl groups include, but are not limited to, unsubstituted furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, hydrazine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzo.
  • 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.
  • a thermally deposited and solution treated OLED device can be fabricated using the platinum (II) complex having the above structure.
  • An organic light-emitting device comprising one or more of the above complexes is included.
  • the complex is applied in layers in the device by thermal deposition.
  • the complex is applied in layers in the device by spin coating.
  • the complex is applied in layers in the device by ink jet printing.
  • the device emits yellow-green color when a current is applied.
  • the organometallic complex of the present invention has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can manufacture a yellow-green light OLED device with high luminous efficiency and low roll-off.
  • Figure 1 is a schematic view showing the structure of an organic electroluminescent device of the present invention.
  • Pt(II) complex of the examples a clear yellow-green light emission was exhibited in the dichloromethane solution solution, with a wavelength ranging from 528 to 531 nm.
  • Pt-0 is a reference O ⁇ N ⁇ C ⁇ O type yellow-green light material. As shown in the following table:
  • the basic structural model of the device was: ITO/HTL-1 (60 nm) / EML-1: Pt (II) (40 nm) / ETL - 1 (30 nm) / LiF (1 nm) / Al (80 nm).
  • the transparent anodized indium tin oxide (ITO, 20) (10 ⁇ /sq) glass substrate 10 was ultrasonically washed with acetone, ethanol, and distilled water in this order, and then treated with oxygen plasma for 5 minutes.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus.
  • the control system pressure is 10 -6 torr.
  • a luminescent layer material (40) EML-1 having a thickness of 40 nm is then evaporated, wherein a certain mass fraction of platinum (II) complex dopant is doped.
  • an electron transport layer (50) material ETL-1 having a thickness of 30 nm was evaporated.
  • LiF having a thickness of 1 nm was evaporated as an electron injecting layer (60).
  • the structure and fabrication method of the device are identical, except that the organometallic complexes Pt-0, TM-1, TM-2, TM-3, TM-4 are sequentially used as dopants and impurity concentrations in the light-emitting layer.
  • TM-4 Compared with Pt-0, TM-1, TM-2 and TM-3, TM-4 has a large sterically hindered group in space, which can effectively reduce the aggregation between molecules, avoid the formation of exciplex and improve luminescence. Efficiency, and thus TM-4 has the best performance on the same device. At the same time, TM-1, TM-2, TM-3 have different degrees of performance improvement relative to Pt-0, indicating O ⁇ N ⁇ C ⁇ N tetradentate platinum (II) based on oxazole, thiazole and imidazole. The complex has a broad application prospect and commercial value.
  • II O ⁇ N ⁇ C ⁇ N tetradentate platinum

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Abstract

The present invention relates to a tetradentate platinum (II) complex material based on oxazole, thiazole or imidazole and a use. The complex has the configuration of O^N^C^N, and the structure thereof is as shown in formula (1), wherein A1-A4 are of a substituted or unsubstituted five-membered ring, six-membered ring, and fused ring structure; X is oxygen, sulfur or substituted nitrogen (-NR0), R0 is one or more R-substituted or unsubstituted C1-C8 alkyls, C5-C20 aryls or heteroaryl groups, and R is halogen, a C1-C4 alkyl, diphenylamino, carbazolyl, or fluorenyl. The complex may be applied in the field of OLEDs as a phosphorescent doping material. The organic metal complex has a high fluorescence quantum efficiency, good thermal stability and a low quenching constant, and can be used to manufacture a yellow-green light OLED device with a high light emission efficiency and a low roll-off.

Description

一种基于恶唑、噻唑或咪唑的四齿铂(II)配合物材料及应用Four-tooth platinum (II) complex material based on oxazole, thiazole or imidazole and application thereof 技术领域Technical field
本发明涉及一种新型基于恶唑、噻唑和咪唑的四齿铂(II)配合物金属有机材料，主要是用于OLED发光器件中，作为发光层中的磷光掺杂材料。The invention relates to a novel tetradentate platinum (II) complex metal organic material based on oxazole, thiazole and imidazole, which is mainly used in an OLED light-emitting device as a phosphorescent dopant material in a light-emitting layer.
背景技术Background technique
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，由美籍华裔教授邓青云(Ching W.Tang)于1979年在实验室中发现。OLED显示技术具有自发光、广视角、几乎无穷高的对比度、较低耗电、极高反应速度等优点，尤其是OLED具有潜在的柔性可折叠特性，因而一直受到广泛的关注与研究，但是OLED存在使用寿命短、色彩纯度差、易老化等缺点，阻碍了OLED技术的大规模应用。因此，设计新型的OLED材料，则是OLED领域研究的重点与难点。Organic Light-Emitting Diode (OLED), also known as organic electro-laser display, organic light-emitting semiconductor, was discovered in the laboratory in 1979 by Chinese-American professor Ching W. Tang. OLED display technology has the advantages of self-luminous, wide viewing angle, almost infinite contrast, low power consumption, high reaction speed, etc. Especially, OLED has potential flexible folding characteristics, and thus has been widely concerned and studied, but OLED The shortcomings of short service life, poor color purity, and aging are hindering the large-scale application of OLED technology. Therefore, designing new OLED materials is the focus and difficulty of OLED research.
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。一般而言，常见的四齿配体主要有O^N^N^O，O^N^C^O，O^N^C^N等类型。其中，O^N^N^O类四齿铂(II)配合物主要为席夫碱(Schiff base)l类，较为常见，但稳定性相对较差；O^N^C^O类四齿铂(II)配合物相对较为稳定，但性能有待提升。本发明中，设计和合成的N^N^N^O构型四齿铂(II)配合物，则是一种新型配位模式，表现出了较好的稳定性和发光性能。其中，O^N^N^O类四齿铂(II)配合物主要为席夫碱(Schiff base)类，较为常见，但稳定性相对较差；O^N^C^O类和O^N^C^N四齿铂(II)配合物相对较为稳定，但性能有待提升。其中，一般的O^N^C^N构型四齿铂(II)配合物，其结构主要是以六元芳香环配体为主。在本发明专利中，则是设计合成了一种新型的基于五元芳香环衍生物恶唑、噻唑和咪唑的四齿铂(II)配合物，并表现出了较好的稳定性和发光性能。Among them, platinum (II)-based phosphorescent OLED materials have shown good display performance in recent years. Platinum (II) is generally a tetracoordinated site, and a metal organoplatinum (II) complex having a unique configuration can be formed by designing a tetradentate ligand. In general, the common tetradentate ligands are mainly O^N^N^O, O^N^C^O, O^N^C^N and the like. Among them, O^N^N^O tetradentate platinum (II) complexes are mainly Schiff bases, which are relatively common, but the stability is relatively poor; O^N^C^O four teeth Platinum (II) complexes are relatively stable, but performance needs to be improved. In the present invention, the designed and synthesized N^N^N^O configuration tetradentate platinum (II) complex is a novel coordination mode, showing good stability and luminescence properties. Among them, O^N^N^O tetradentate platinum (II) complexes are mainly Schiff bases, which are relatively common, but the stability is relatively poor; O^N^C^O and O^ The N^C^N tetradentate platinum (II) complex is relatively stable, but its performance needs to be improved. Among them, the general O^N^C^N configuration of tetradentate platinum (II) complexes, the structure of which is mainly composed of six-membered aromatic ring ligands. In the patent of the present invention, a novel tetradentate platinum (II) complex based on a five-membered aromatic ring derivative oxazole, thiazole and imidazole is designed and synthesized, and exhibits good stability and luminescence properties. .
发明内容Summary of the invention
本发明设计了一种新型基于恶唑、噻唑和咪唑的O^N^C^N四齿铂(II)配合物材料，可以作为一种磷光掺杂材料应用在OLED领域。该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，可以制造高效率低效率滚降的黄绿色光OLED器件。The invention designs a novel O^N^C^N tetradentate platinum (II) complex material based on oxazole, thiazole and imidazole, and can be applied as a phosphorescent dopant material in the field of OLED. The organometallic complex has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can manufacture a yellow-green light OLED device with high efficiency and low efficiency roll-off.
本发明还提供该新型铂(II)配合物的制备方法。The invention also provides a preparation method of the novel platinum (II) complex.
一种基于恶唑、噻唑和咪唑的O^N^C^N四齿铂(II)配合物材料,其结构如式(1)所示：An O^N^C^N tetradentate platinum(II) complex material based on oxazole, thiazole and imidazole, the structure of which is shown in formula (1):
Figure PCTCN2018122965-appb-000001
Figure PCTCN2018122965-appb-000001
其中，A 1－A 4为取代的或非取代的五元环、六元环、稠环结构；X为氧，硫或者取代的氮(-NR 0)，R 0为一个或多个R取代或未取代C1-C8烷基、C5-C20的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein, A 1 -A 4 is a substituted or unsubstituted five-membered ring, six-membered ring, fused ring structure; X is oxygen, sulfur or substituted nitrogen (-NR 0 ), and R 0 is substituted by one or more R Or unsubstituted C1-C8 alkyl, C5-C20 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamino, oxazolyl, fluorenyl.
其结构可以优选为如式(2)所示的结构：The structure may preferably be a structure as shown in the formula (2):
Figure PCTCN2018122965-appb-000002
Figure PCTCN2018122965-appb-000002
其中R 1－R 14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、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 14相互通过共价键连接成环；其中X 1－X 22为碳，X为氧，硫或者取代的氮-NR 0，R 0为一个或多个R取代或未取代C1-C6烷基、C5-C15的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen-NR 0 , R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamine Base, carbazolyl, fluorenyl.
优选：其中R 1－R 14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 14相互通过共价键连接成环，X为氧，硫或者取代的氮-NR 0，R 0为下列取代基： Preferably, wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl having 1 to 10 C atoms, and having 5 to 20 C atoms Halogen or one or more C1-C4 alkyl-substituted or unsubstituted aryl groups, 5-20 C atoms substituted by halogen or one or more C1-C4 alkyl groups or unsubstituted heteroaryl groups, or phases The adjacent R 1 -R 14 are bonded to each other by a covalent bond, X is oxygen, sulfur or substituted nitrogen -NR 0 , and R 0 is the following substituent:
Figure PCTCN2018122965-appb-000003
Figure PCTCN2018122965-appb-000003
Figure PCTCN2018122965-appb-000004
Figure PCTCN2018122965-appb-000004
优选：Preferred:
Figure PCTCN2018122965-appb-000005
Figure PCTCN2018122965-appb-000005
其中R' 1～R' 4为独立地为氢、含1－6个C原子的饱和烷基、二芳胺基、含5－10个C原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个C1－C4烷基取代的或未取代的杂芳基。 Wherein R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
优选：R' 1～R' 4的4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原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个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或含1－6个C原子的饱和烷基。 Preferably, among the 4 groups of R' 1 to R' 4 , 0-3 of the groups are independently represented by a diarylamine group, 5-10 C atoms are halogenated or one to three C1-C4 alkane a substituted or unsubstituted aryl group, a halogen-containing or one to three C1-C4 alkyl-substituted or unsubstituted heteroaryl group having 5 to 10 C atoms, and the other groups are independently represented as hydrogen or A saturated alkyl group of 1 to 6 C atoms.
优选：R' 2～R' 4的中的一个基团选自二苯胺基、苯、吡啶、咔唑基、异丙基或叔丁基，其它基团独立的表示为氢；R' 1表示为氢。 Preferably, one of R' 2 to R' 4 is selected from the group consisting of diphenylamine, benzene, pyridine, carbazolyl, isopropyl or tert-butyl, and the other groups are independently represented by hydrogen; R' 1 represents It is hydrogen.
优选：R' 1～R' 4表示为氢；X为氧，硫或者取代的氮-NR 0，R 0为C1－C8的烷基。 Preferably, R' 1 to R' 4 are represented by hydrogen; X is oxygen, sulfur or substituted nitrogen -NR 0 , and R 0 is a C1-C8 alkyl group.
如下所示的具体实例，X为O、S、NR 0，包括但不限于以下结构： In the specific example shown below, X is O, S, NR 0 , including but not limited to the following structure:
Figure PCTCN2018122965-appb-000006
Figure PCTCN2018122965-appb-000006
Figure PCTCN2018122965-appb-000007
Figure PCTCN2018122965-appb-000007
Figure PCTCN2018122965-appb-000008
Figure PCTCN2018122965-appb-000008
Figure PCTCN2018122965-appb-000009
Figure PCTCN2018122965-appb-000009
Figure PCTCN2018122965-appb-000010
Figure PCTCN2018122965-appb-000010
Figure PCTCN2018122965-appb-000011
Figure PCTCN2018122965-appb-000011
Figure PCTCN2018122965-appb-000012
Figure PCTCN2018122965-appb-000012
Figure PCTCN2018122965-appb-000013
Figure PCTCN2018122965-appb-000013
优选：其具有如下结构：Preferably: it has the following structure:
Figure PCTCN2018122965-appb-000014
Figure PCTCN2018122965-appb-000014
上述配合物的前体，即配体，其结构式如下：The precursor of the above complex, ie, the ligand, has the following structural formula:
Figure PCTCN2018122965-appb-000015
Figure PCTCN2018122965-appb-000015
其中，A 1－A 4为取代的或非取代的五元环、六元环、稠环结构；X为氧，硫或者取代的氮(-NR 0)，R 0为取代基，R 0为一个或多个R取代或未取代C1-C8烷基、C5-C20的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein, A 1 -A 4 is a substituted or unsubstituted five-membered ring, a six-membered ring, a fused ring structure; X is oxygen, sulfur or a substituted nitrogen (-NR 0 ), and R 0 is a substituent, and R 0 is One or more R substituted or unsubstituted C1-C8 alkyl, C5-C20 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamino, oxazolyl, fluorenyl.
优选：Preferred:
Figure PCTCN2018122965-appb-000016
Figure PCTCN2018122965-appb-000016
其中R 1－R 14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、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 14相互通过共价键连接成环；其中X 1－X 22为碳，X为氧，硫或者取代的氮-NR 0，R 0为一个或多个R取代或未取代C1-C6烷基、C5-C15的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen-NR 0 , R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamine Base, carbazolyl, fluorenyl.
更优选：More preferably:
Figure PCTCN2018122965-appb-000017
Figure PCTCN2018122965-appb-000017
其中R' 1～R' 4为独立地为氢、含1－6个C原子的饱和烷基、二芳胺基、含5－10个C原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个C1－C4烷基取代的或未取代的杂芳基。 Wherein R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
上述配合物的制备方法：Preparation method of the above complex:
如下式所示，对于恶唑和噻唑类，即当X＝O,S时，底物A1与芳香醛A2反应得到底物A3，A3继续反应得到相应的频哪醇酯A4，A4与A5经Suzuki反应得到相应的底物A6，A6经脱甲基反应后得到配体A7，A7与K 2PtCl 4反应即得到相应的目标产物A。其中，R' 1～R' 5为芳香或非芳香取代基。 As shown in the following formula, for oxazole and thiazole, that is, when X = O, S, substrate A1 reacts with aromatic aldehyde A2 to obtain substrate A3, and A3 continues to react to obtain the corresponding pinacol ester A4, A4 and A5. The Suzuki reaction gives the corresponding substrate A6. After demethylation of A6, the ligand A7 is obtained, and A7 reacts with K 2 PtCl 4 to obtain the corresponding target product A. Wherein R' 1 to R' 5 are aromatic or non-aromatic substituents.
Figure PCTCN2018122965-appb-000018
Figure PCTCN2018122965-appb-000018
如下图所示，对于咪唑类(X＝NR 0)，邻苯二铵B1与芳香醛B2反应得到B3,B3在碱性条件下与卤代物反应得到B4，B4进一步反应得到相应的频哪醇酯B5，B5与B6经Suzuki反应得到底物B7，B7经脱甲基后得到配体B8，B8与K 2PtCl 4反应即得到相应的目标产物B。 As shown in the figure below, for imidazoles (X=NR 0 ), o-phenylammonium B1 reacts with aromatic aldehyde B2 to obtain B3. B3 reacts with halogenated compounds under basic conditions to obtain B4, and B4 further reacts to obtain the corresponding pinacol. The ester B5, B5 and B6 are reacted by Suzuki to obtain the substrate B7, and the B7 is demethylated to obtain the ligand B8, and the B8 reacts with K 2 PtCl 4 to obtain the corresponding target product B.
Figure PCTCN2018122965-appb-000019
Figure PCTCN2018122965-appb-000019
为了本申请的目的，除非另有指明，术语卤素、烷基、环烷基、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：For the purposes of this application, the terms halogen, alkyl, cycloalkyl, aryl, acyl, alkoxy, and heterocyclic aromatic or heterocyclic aromatic groups may have the following meanings, unless otherwise indicated:
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。The above halogen or halogen includes fluorine, chlorine, bromine and iodine, preferably F, Cl, Br, particularly preferably F or Cl, most preferably F.
上述共价键连接成环、芳基、杂芳基或稠环结构包括具有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，优选可被取代的或是未取代C 5，C 6芳基或芴基；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。杂芳基，优选含至少一个氮原子的杂芳基，特别优选吡啶基；不饱和烷基优选烯基，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。 The above covalent bond is bonded to a ring, aryl, heteroaryl or fused ring structure comprising from 5 to 30 carbon atoms, preferably from 5 to 20 carbon atoms, more preferably from 5 to 10 carbon atoms and from one aromatic ring or more An aryl group consisting of a fused aromatic ring. Suitable aryl groups are, for example, phenyl, naphthyl, acenaphthenyl, acenaphthenyl, fluorenyl, fluorenyl, phenalenyl. The aryl group may be unsubstituted (i.e., all carbon atoms capable of substituting a hydrogen atom) 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 having from 1 to 20, from 1 to 10 or from 1 to 8 carbon atoms, particularly preferably methyl, ethyl or isopropyl Or a tert-butyl group; an aryl group, preferably a substituted or unsubstituted C 5 , C 6 aryl or anthracenyl group; the aryl group particularly preferably has a substituent selected from the group consisting of F and a t-butyl group, preferably a given aryl group or an aryl group which is a C 5 ,C 6 aryl group optionally substituted by at least one of the above substituents, and a C 5 , C 6 aryl group particularly preferably has 0, 1 or 2 of the above substituents, C 5 , C 6 aryl is especially particularly preferably unsubstituted phenyl or substituted phenyl, such as biphenyl, phenyl which is preferably substituted in the meta position by two t-butyl groups. a heteroaryl group, preferably a heteroaryl group containing at least one nitrogen atom, particularly preferably a pyridyl group; an unsaturated alkyl group is preferably an alkenyl group, preferably an alkenyl group having one double bond, particularly preferably having a double bond and 1-8 carbon atoms Alkenyl.
上述烷基或烷基部分包括具有1－20个碳原子，优选1－10个碳原子，优选1－6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。The above alkyl or alkyl moiety includes an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The alkyl group may be branched or linear, or may be cyclic, and may be interrupted by one or more heteroatoms, preferably N, O or S. Moreover, the alkyl group may be substituted by one or more halogens or the above-mentioned substituents with respect to the aryl group. Likewise, it is possible for the alkyl group to have one or more aryl groups, all of which are suitable for this purpose, the alkyl group being particularly preferred from methyl, ethyl, isopropyl, n-propyl, Isobutyl, n-butyl, tert-butyl, sec-butyl, isopentyl, cyclopropyl, cyclopentyl, cyclohexyl.
上述酰基是以单键连接至CO基团的，如本文所用的烷基。The above acyl group is an alkyl group which is bonded to a CO group by a single bond, as used herein.
上述烷氧基是以单键与氧直接相连的，如本文所用的烷基。The above alkoxy group is directly bonded to oxygen as a single bond, as used herein.
上述杂芳基被理解为与芳基、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，所述杂芳族体系或杂环芳族基团可被一个或多个提到的关于芳基的取代基所取代。 The above heteroaryl is understood to be related to an aryl group, a C 3 -C 8 ring group, and further comprises an oxygen or sulfur atom or a combination of 1 to 4 nitrogen atoms or an oxygen or sulfur atom and up to two nitrogen atoms, And their substituted and benzopyridinium-fused derivatives, for example, via one of the ring-forming carbon atoms, which may be referred to by one or more of the hetero-aromatic groups Substituted by an aryl group.
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。 In certain embodiments, a heteroaryl group can be a five or six membered aromatic heterocyclic ring system containing the above independent zero, one or two substituents. Typical examples of heteroaryl groups include, but are not limited to, unsubstituted furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, hydrazine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzo. Thiazole, isothiazole, imidazole, benzimidazole, pyrazole, oxazole, tetrazole, quinoline, isoquinoline, pyridazine, pyrimidine, purine and pyrazine, furan, 1,2,3-diazole, 1, 2,3-thiadiazole, 1,2,4-thiadiazole, triazole, benzotriazole, acridine, benzoxazole, diazole, benzopyrazole, quinolizine, porphyrin, pyridazine, Quinazole and quinoxaline and their mono- or di-substituted derivatives. In certain embodiments, 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.
上述配合物在OLED发光器件中的应用。The use of the above complexes in OLED light-emitting devices.
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。A thermally deposited and solution treated OLED device can be fabricated using the platinum (II) complex having the above structure.
包括含有一种或多种上述配合物的有机发光器件。An organic light-emitting device comprising one or more of the above complexes is included.
其中通过热沉积在该器件中以层形式施加该配合物。The complex is applied in layers in the device by thermal deposition.
其中通过旋涂在该器件中以层形式施加该配合物。The complex is applied in layers in the device by spin coating.
其中通过喷墨打印在该器件中以层形式施加该配合物。The complex is applied in layers in the device by ink jet printing.
上述有机发光器件，在施加电流时该器件发射为黄绿色。In the above organic light-emitting device, the device emits yellow-green color when a current is applied.
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、低滚降的黄绿色光OLED器件。The organometallic complex of the present invention has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can manufacture a yellow-green light OLED device with high luminous efficiency and low roll-off.
附图说明DRAWINGS
图1本发明的有机电致发光器件的结构示意图。Figure 1 is a schematic view showing the structure of an organic electroluminescent device of the present invention.
具体实施方式Detailed ways
下面结合实施例对本发明做进一步的详细说明。The present invention will be further described in detail below with reference to the embodiments.
实施例1：Example 1:
Figure PCTCN2018122965-appb-000020
Figure PCTCN2018122965-appb-000020
化合物1的合成:取5.45g(50mmol)邻氨基苯酚溶于125mL甲苯中，加入9.25g(1.0eq.,50mmol)间溴苯甲醛，在室温下搅拌1hr，然后加热至110℃回流反应12hr。反应停止后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体9.32g，产率68％，纯度99.0％。Synthesis of Compound 1: 5.45 g (50 mmol) of o-aminophenol was dissolved in 125 mL of toluene, 9.25 g (1.0 eq., 50 mmol) of m-bromobenzaldehyde was added, and the mixture was stirred at room temperature for 1 hr, and then heated to 110 ° C for reflux for 12 hr. After the reaction was stopped, the mixture was cooled to room temperature, and the solvent was evaporated to dryness, and then, the mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography gave 9.32 g of a white solid, yield 68%, purity 99.0%.
化合物2的合成:取5.48g(20.0mmol)化合物1，联硼酸频哪醇酯6.35g(1.25eq.,25.0mmol)，碳酸钾2.59g(1.25eq.,25.0mmol)和Pd(dppf)Cl 2 292mg(0.02eq.,0.4mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入二氧六环150mL，加热至85℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体5.26g，产率82％，纯度99.5％。 Synthesis of Compound 2: 5.48 g (20.0 mmol) of Compound 1, bisboronic acid pinacol ester 6.35 g (1.25 eq., 25.0 mmol), potassium carbonate 2.59 g (1.25 eq., 25.0 mmol) and Pd(dppf)Cl. 2 292 mg (0.02 eq., 0.4 mmol) was placed in a three-necked flask, vacuum-replaced with nitrogen for several times, then 150 mL of dioxane was charged and heated to 85 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on ethyl acetate afforded 5.26 g of white solid.
化合物3的合成:取11.85g(50.0mmol)化合物2,6-二溴吡啶，2-甲氧基苯硼酸7.60g(1.0eq.,50.0mmol)，碳酸钾6.48g(1.25eq.,62.5mmol)和Pd(OAc) 2 224mg(0.02eq.,1mmol)，PPh 3 1.31g(0.1eq.,5mmol)加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈150mL，甲醇50mL,加热至60℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体9.90g，产率75％，纯度99.0％。 Synthesis of Compound 3: 11.85 g (50.0 mmol) of compound 2,6-dibromopyridine, 2.70 g of 2-methoxyphenylboronic acid (1.0 eq., 50.0 mmol), potassium carbonate 6.48 g (1.25 eq., 62.5 mmol) And Pd(OAc) 2 224 mg (0.02 eq., 1 mmol), PPh 3 1.31 g (0.1 eq., 5 mmol) was added to a three-necked flask, vacuum-replaced with nitrogen for several times, and then 150 mL of acetonitrile and 50 mL of methanol were injected. , heated to 60 ° C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 9.90 g of a white solid, yield 75%, purity 99.0%.
化合物4的合成：取4.82g(15.0mmol)化合物2，化合物3 3.96g(1.0eq.,15.0mmol)，，碳酸钾2.59g(1.25eq.,18.75mmol)和Pd(PPh 3) 4 347mg(0.02eq.,0.3mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈100mL和50mL甲醇，加热至60℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体3.97g，产率70％，纯度99.9％。 Synthesis of Compound 4: 4.82 g (15.0 mmol) of Compound 2, Compound 3 3.96 g (1.0 eq., 15.0 mmol), potassium carbonate 2.59 g (1.25 eq., 18.75 mmol) and Pd(PPh 3 ) 4 347 mg ( 0.02 eq., 0.3 mmol), which was placed in a three-necked flask, was evacuated and purged with nitrogen several times, then 100 mL of acetonitrile and 50 mL of methanol were poured and heated to 60 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 3.97 g of white solid, yield 70%, purity 99.9%.
化合物5的合成：取3.03g(8.0mmol)化合物4，吡啶盐酸盐45g(PyHCl)，加入到三颈烧瓶中，抽真空通入氮气置换多次，在氮气保护下加热至190℃，反应4hr后，冷却至室温，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸 除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体2.51g，产率86％，纯度99.9％。质谱(ESI -)([M-H] -)C 24H 15N 3O 2理论值:363.12；实测值:363.11。 Synthesis of compound 5: 3.03 g (8.0 mmol) of compound 4, pyridine hydrochloride 45 g (PyHCl), added to a three-necked flask, vacuumed and replaced with nitrogen several times, heated to 190 ° C under nitrogen atmosphere, reaction After 4 hr, it was cooled to room temperature, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. The solid was 2.51 g, the yield was 86%, and the purity was 99.9%. Mass spectrum (ESI -) ([MH] -) C 24 H 15 N 3 O 2 Calculated: 363.12; Found: 363.11.
化合物TM-1的合成：取1.09g(3.0mmol)化合物5和492mg无水醋酸钠(2.0eq.,6.0mmol)溶于35mL DMSO中，搅拌，加热至80℃，然后加入四氯铂酸钾1.25g(1.0eq.,3.0mmol)，抽真空通入氮气置换数次，升温到120℃反应5hr。反应结束后，趁热加入100ml水，过滤，收集固体，用适量水和甲醇洗涤，将得到的固体用甲苯重结晶，然后真空升华得到黄色固体1.21g，总产率72％，纯度99.9％。质谱(ESI -)([M-H] -)C 24H 13N 3O 2Pt理论值:556.07；实测值:556.05。 Synthesis of Compound TM-1: 1.09 g (3.0 mmol) of Compound 5 and 492 mg of anhydrous sodium acetate (2.0 eq., 6.0 mmol) were dissolved in 35 mL of DMSO, stirred, heated to 80 ° C, and then potassium tetrachloroplatinate was added. 1.25 g (1.0 eq., 3.0 mmol) was purged several times with nitrogen and heated to 120 ° C for 5 hr. After completion of the reaction, 100 ml of water was added while hot, and the solid was collected, washed with water and methanol, and the obtained solid was recrystallized from toluene, and then sublimated in vacuo to give 1.21 g of a yellow solid, yield 72%, purity 99.9%. Mass spectrum (ESI -) ([MH] -) C 24 H 13 N 3 O 2 Pt Calculated: 556.07; Found: 556.05.
实施例2：Example 2:
Figure PCTCN2018122965-appb-000021
Figure PCTCN2018122965-appb-000021
化合物5的合成:取5.45g(50mmol)邻氨基噻吩溶于125mL甲苯中，加入9.25g(1.0eq.,50mmol)间溴苯甲醛，在室温下搅拌1hr，然后加热至110℃回流反应12hr。反应停止后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体13.05g，产率90％，纯度99.0％。Synthesis of Compound 5: 5.45 g (50 mmol) of o-aminothiophene was dissolved in 125 mL of toluene, 9.25 g (1.0 eq., 50 mmol) of m-bromobenzaldehyde was added, and the mixture was stirred at room temperature for 1 hr, and then heated to 110 ° C for reflux for 12 hr. After the reaction was stopped, the mixture was cooled to room temperature, and the solvent was evaporated to dryness, and then, the mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography gave 13.05 g of a white solid, yield 90%, purity 99.0%.
化合物6的合成:取5.80g(20.0mmol)化合物5，联硼酸频哪醇酯6.35g(1.25eq.,25.0mmol)，碳酸钾2.59g(1.25eq.,25.0mmol)和Pd(dppf)Cl 2 292mg(0.02eq.,0.4mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈二氧六环150mL，加热至85℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体5.80g，产率86％，纯度99.5％。 Synthesis of Compound 6: 5.80 g (20.0 mmol) of Compound 5, bis-boronic acid pinacol ester 6.35 g (1.25 eq., 25.0 mmol), potassium carbonate 2.59 g (1.25 eq., 25.0 mmol) and Pd(dppf)Cl 2 292 mg (0.02 eq., 0.4 mmol) was placed in a three-necked flask, vacuum-replaced with nitrogen for several times, and then 150 mL of acetonitrile dioxane was injected and heated to 85 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on ethyl acetate gave a white solid 5.80 g, yield 86%,
化合物7的合成：取5.06g(15.0mmol)化合物6，化合物3 3.96g(1.0eq.,15.0mmol)，，碳酸钾2.59g(1.25eq.,18.75mmol)和Pd(PPh 3) 4 347mg(0.02eq.,0.3mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈100mL和50mL甲醇，加热至60℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体4.44g，产率75％，纯度99.9％。 Synthesis of Compound 7: 5.06 g (15.0 mmol) of Compound 6, Compound 3 3.96 g (1.0 eq., 15.0 mmol), potassium carbonate 2.59 g (1.25 eq., 18.75 mmol) and Pd(PPh 3 ) 4 347 mg ( 0.02 eq., 0.3 mmol), which was placed in a three-necked flask, was evacuated and purged with nitrogen several times, then 100 mL of acetonitrile and 50 mL of methanol were poured and heated to 60 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on ethyl acetate gave a white solid 4.44 g, yield 75%, purity 99.9%.
化合物8的合成：取3.16g(8.0mmol)化合物7，吡啶盐酸盐45g(PyHCl)，加入到三颈烧瓶中，抽真空通入氮气置换多次，在氮气保护下加热至190℃，反应4hr后，冷却至室温，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体2.50g，产率82％，纯度99.9％。质谱(ESI -)([M-H] -)C 24H 15N 3OS理论值:380.10；实测值:380.07。 Synthesis of compound 8: 3.16 g (8.0 mmol) of compound 7, pyridine hydrochloride 45 g (PyHCl), added to a three-necked flask, vacuumed and replaced with nitrogen several times, heated to 190 ° C under nitrogen atmosphere, reaction After 4 hr, it was cooled to room temperature, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. The solid was 2.50 g, the yield was 82%, and the purity was 99.9%. Mass spectrum (ESI -) ([MH] -) C 24 H 15 N 3 OS Calculated: 380.10; Found: 380.07.
化合物(TM-2)的合成：取1.14g(3.0mmol)化合物8和492mg无水醋酸钠(2.0eq.,6.0mmol)溶于35mL DMSO中，搅拌，加热至80℃，然后加入四氯铂酸钾1.25g(1.0eq.,3.0mmol)，抽真空通入氮气置换数次，升温到120℃反应5hr。反应结束后，趁热加入100ml水，过滤，收集固体，用适量水和甲醇洗涤，将得到的固体用甲苯重结晶，然后真空升华得 到黄色固体1.12g，总产率68％，纯度99.9％。质谱(ESI -)([M-H] -)C 24H 14N 3OSPt理论值:572.04；实测值:572.03。 Synthesis of Compound (TM-2): 1.14 g (3.0 mmol) of Compound 8 and 492 mg of anhydrous sodium acetate (2.0 eq., 6.0 mmol) were dissolved in 35 mL of DMSO, stirred, heated to 80 ° C, then tetrachloroplatinum was added Potassium acid 1.25 g (1.0 eq., 3.0 mmol) was introduced into the vacuum several times with a vacuum, and the temperature was raised to 120 ° C for 5 hr. After completion of the reaction, 100 ml of water was added while hot, and the solid was collected, washed with water and methanol, and the obtained solid was recrystallized from toluene, and then sublimated in vacuo to give 1.12 g of a yellow solid. Mass spectrum (ESI -) ([MH] -) C 24 H 14 N 3 OSPt Calculated: 572.04; Found: 572.03.
实施例3：Example 3:
Figure PCTCN2018122965-appb-000022
Figure PCTCN2018122965-appb-000022
化合物9的合成:取5.41g(50mmol)邻氨基苯酚溶于150mL乙腈中，加入9.25g(1.0 eq.,50mmol)间溴苯甲醛，在室温下搅拌1hr，然后加入36％盐酸16.5mL和30％双氧水41.1mL，室温搅拌反应12hr。反应停止后，加入饱和碳酸钠溶液调节pH至中性，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体11.74g，产率86％，纯度99.0％。Synthesis of Compound 9: 5.41 g (50 mmol) of o-aminophenol was dissolved in 150 mL of acetonitrile, 9.25 g (1.0 eq., 50 mmol) of m-bromobenzaldehyde was added, and stirred at room temperature for 1 hr, then 36% hydrochloric acid 16.5 mL and 30 were added. 41.1 mL of hydrogen peroxide was stirred at room temperature for 12 hr. After the reaction was stopped, the saturated sodium carbonate solution was added to adjust the pH to neutrality, and then an appropriate amount of water and ethyl acetate were added to extract, and the organic phase was collected. After drying over anhydrous magnesium sulfate, an appropriate amount of silica gel was added, and the solvent was removed by rotary evaporation using n-hexane/ethyl acetate. Column chromatography of the ester system gave 11.74 g of a white solid, yield 86%, purity 99.0%.
化合物10的合成:取5.46g(20.0mmol)化合物9，溶于60mL N,N-二甲基甲酰胺中，然后在冰水浴条件下分批次加入60％NaH 4.80g(6.0eq.,120.0mmol)，搅拌反应2hr后加入正溴丁烷3.29g(24.0mmol)。反应12hr后，使用适量冰水猝灭反应，然后再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体6.26g，产率95％，纯度99.5％。Synthesis of compound 10: 5.46 g (20.0 mmol) of compound 9 was dissolved in 60 mL of N,N-dimethylformamide, and then 60% NaH 4.80 g (6.0 eq., 120.0) was added in portions in an ice water bath. (mmol), the reaction was stirred for 2 hr and then 3.29 g (24.0 mmol) of n-bromobutane was added. After reacting for 12 hr, the reaction was quenched with an appropriate amount of ice water, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. Column chromatography gave 6.26 g of a white solid, yield 95%, purity 99.5%.
化合物11的合成:取4.94g(15.0mmol)化合物10，联硼酸频哪醇酯4.76g(1.25eq.,18.75mmol)，碳酸钾1.94g(1.25eq.,18.75mmol)和Pd(dppf)Cl 2 219mg(0.02eq.,0.3mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈二氧六环150mL，加热至85℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体4.63g，产率82％，纯度99.5％。 Synthesis of Compound 11: 4.94 g (15.0 mmol) of Compound 10, 4.76 g of diboronic acid pinacol ester (1.25 eq., 18.75 mmol), 1.94 g of potassium carbonate (1.25 eq., 18.75 mmol) and Pd(dppf)Cl. 2 219 mg (0.02 eq., 0.3 mmol) was placed in a three-necked flask, vacuum-replaced several times with nitrogen, and then 150 mL of acetonitrile dioxane was injected and heated to 85 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 4.63 g of white solid.
化合物12的合成：取3.76g(10.0mmol)化合物11，化合物3 2.62g(1.0eq.,10.0mmol)，，碳酸钾1.73g(1.25eq.,12.5mmol)和Pd(PPh 3) 4 231mg(0.02eq.,0.2mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈100mL和50mL甲醇，加热至60℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体3.47g，产率80％，纯度99.9％。 Synthesis of compound 12: 3.76 g (10.0 mmol) of compound 11, 3.62 g (1.0 eq., 10.0 mmol), potassium carbonate 1.73 g (1.25 eq., 12.5 mmol) and Pd(PPh 3 ) 4 231 mg ( 0.02 eq., 0.2 mmol), which was added to a three-necked flask, was evacuated and purged with nitrogen several times, and then 100 mL of acetonitrile and 50 mL of methanol were poured and heated to 60 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 3.47 g of a white solid.
化合物13的合成：取2.17g(5.0mmol)化合物12，吡啶盐酸盐35g(PyHCl)，加入到三颈烧瓶中，抽真空通入氮气置换多次，在氮气保护下加热至190℃，反应4hr后，冷却至室温，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体1.64g，产率78％，纯度99.9％。质谱(ESI -)([M-H] -)C 28H 24N 3O理论值:418.20；实测值:418.18。 Synthesis of compound 13: 2.17 g (5.0 mmol) of compound 12, pyridine hydrochloride 35 g (PyHCl), added to a three-necked flask, vacuumed and replaced with nitrogen several times, heated to 190 ° C under nitrogen atmosphere, reaction After 4 hr, it was cooled to room temperature, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. The solid was 1.64 g, the yield was 78%, and the purity was 99.9%. Mass spectrum (ESI -) ([MH] -) C 28 H 24 N 3 O Calculated: 418.20; Found: 418.18.
化合物(TM-3)的合成：取1.05g(2.5mmol)化合物13和410mg无水醋酸钠(2.0eq.,5.0mmol)溶于30mL DMSO中，搅拌，加热至80℃，然后加入四氯铂酸钾1.04g(1.0eq.,2.5mmol)，抽真空通入氮气置换数次，升温到120℃反应5hr。反应结束后，趁热加入100ml水，过滤，收集固体，用适量水和甲醇洗涤，将得到的固体用甲苯重结晶，然后真空升华得到黄色固体951mg，总产率62％，纯度99.9％。质谱(ESI -)([M-H] -)C 28H 22N 3OPt理论值:610.14；实测值::610.12。 Synthesis of Compound (TM-3): 1.05 g (2.5 mmol) of Compound 13 and 410 mg of anhydrous sodium acetate (2.0 eq., 5.0 mmol) were dissolved in 30 mL of DMSO, stirred, heated to 80 ° C, then tetrachloroplatinum was added Potassium acid 1.04 g (1.0 eq., 2.5 mmol) was vacuumed several times with nitrogen and heated to 120 ° C for 5 hr. After completion of the reaction, 100 ml of water was added while hot, and the solid was collected, washed with water and methanol, and the obtained solid was recrystallized from toluene, and then sublimated in vacuo to give 951 g of a yellow solid, yield 62%, purity 99.9%. Mass spectrum (ESI -) ([MH] -) C 28 H 22 N 3 OPt Calculated: 610.14; Found 610.12 ::.
实施例4：Example 4:
Figure PCTCN2018122965-appb-000023
Figure PCTCN2018122965-appb-000023
Figure PCTCN2018122965-appb-000024
Figure PCTCN2018122965-appb-000024
化合物15的合成:取5.46g(20.0mmol)化合物9，溶于60mL N,N-二甲基甲酰胺中，然后在冰水浴条件下分批次加入60％NaH 4.80g(6.0eq.,120.0mmol)，搅拌反应2hr后加入化合物14 5.78g(24.0mmol)。反应12hr后，使用适量冰水猝灭反应，然后再加入适 量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体7.80g，产率90％，纯度99.5％。Synthesis of compound 15: 5.46 g (20.0 mmol) of compound 9 was dissolved in 60 mL of N,N-dimethylformamide, and then 60% NaH 4.80 g (6.0 eq., 120.0) was added in portions in an ice water bath. (mmol), the reaction was stirred for 2 hr and then compound 14.78 g (24.0 mmol). After reacting for 12 hr, the reaction was quenched with an appropriate amount of ice water, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. Column chromatography gave 7.80 g of a white solid, yield 90%, purity 99.5%.
化合物16的合成:取6.50g(15.0mmol)化合物15，联硼酸频哪醇酯4.76g(1.25eq.,18.75mmol)，碳酸钾1.94g(1.25eq.,18.75mmol)和Pd(dppf)Cl 2 219mg(0.02eq.,0.3mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈二氧六环150mL，加热至85℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体6.38g，产率86％，纯度99.0％。 Synthesis of compound 16: 6.50 g (15.0 mmol) of compound 15, 4.76 g of diboronic acid pinacol ester (1.25 eq., 18.75 mmol), 1.94 g of potassium carbonate (1.25 eq., 18.75 mmol) and Pd(dppf)Cl. 2 219 mg (0.02 eq., 0.3 mmol) was placed in a three-necked flask, vacuum-replaced several times with nitrogen, and then 150 mL of acetonitrile dioxane was injected and heated to 85 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 6.38 g of a white solid, yield 86%, purity 99.0%.
化合物17的合成：取3.76g(10.0mmol)化合物11，化合物3 2.62g(1.0eq.,10.0mmol)，，碳酸钾1.73g(1.25eq.,12.5mmol)和Pd(PPh 3) 4 231mg(0.02eq.,0.2mmol)，加入到三颈烧瓶中，抽真空通入氮气置换多次，然后注入乙腈100mL和50mL甲醇，加热至60℃。在氮气保护下反应12hr后，冷却至室温，旋蒸除去溶剂，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体3.47g，产率80％，纯度99.9％。 Synthesis of compound 17: 3.76 g (10.0 mmol) of compound 11, 3.62 g (1.0 eq., 10.0 mmol), potassium carbonate 1.73 g (1.25 eq., 12.5 mmol) and Pd(PPh 3 ) 4 231 mg ( 0.02 eq., 0.2 mmol), which was added to a three-necked flask, was evacuated and purged with nitrogen several times, and then 100 mL of acetonitrile and 50 mL of methanol were poured and heated to 60 °C. After reacting under nitrogen for 12 hr, the mixture was cooled to room temperature, and the solvent was evaporated to remove the solvent. The mixture was evaporated to ethyl ether. The organic phase was collected, dried over anhydrous magnesium sulfate, and then evaporated. Column chromatography on an ethyl acetate system gave 3.47 g of a white solid.
化合物18的合成：取2.69g(5.0mmol)化合物17，吡啶盐酸盐35g(PyHCl)，加入到三颈烧瓶中，抽真空通入氮气置换多次，在氮气保护下加热至190℃，反应4hr后，冷却至室温，再加入适量水和乙酸乙酯萃取，收集有机相，无水硫酸镁干燥后加入适量硅胶，旋蒸除去溶剂，使用正己烷/乙酸乙酯体系柱层析，得到白色固体2.36g，产率90％，纯度99.9％。质谱(ESI -)([M-H] -)C 36H 32N 3O理论值:522.26；实测值:522.25。 Synthesis of compound 18: 2.69 g (5.0 mmol) of compound 17, pyridine hydrochloride 35 g (PyHCl), added to a three-necked flask, vacuumed and replaced with nitrogen several times, heated to 190 ° C under nitrogen atmosphere, reaction After 4 hr, it was cooled to room temperature, and then extracted with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. The solid was 2.36 g, the yield was 90%, and the purity was 99.9%. Mass spectrum (ESI -) ([MH] -) C 36 H 32 N 3 O Calculated: 522.26; Found: 522.25.
化合物(TM-4)的合成：取1.31g(2.5mmol)化合物18和410mg无水醋酸钠(2.0eq.,5.0mmol)溶于30mL DMSO中，搅拌，加热至80℃，然后加入四氯铂酸钾1.04g(1.0eq.,2.5mmol)，抽真空通入氮气置换数次，升温到120℃反应5hr。反应结束后，趁热加入100ml水，过滤，收集固体，用适量水和甲醇洗涤，将得到的固体用甲苯重结晶，然后真空升华得到黄色固体985mg，总产率55％，纯度99.9％。质谱(ESI -)([M-H] -)C 36H 30N 3OPt理论值:715.21；实测值:715.19。 Synthesis of compound (TM-4): 1.31 g (2.5 mmol) of compound 18 and 410 mg of anhydrous sodium acetate (2.0 eq., 5.0 mmol) were dissolved in 30 mL of DMSO, stirred, heated to 80 ° C, then tetrachloroplatinum was added Potassium acid 1.04 g (1.0 eq., 2.5 mmol) was vacuumed several times with nitrogen and heated to 120 ° C for 5 hr. After completion of the reaction, 100 ml of water was added while hot, and the solid was collected, washed with water and methanol, and the obtained solid was recrystallized from toluene, and then sublimated in vacuo to give 985 mg of a yellow solid, yield 55%, purity 99.9%. Mass spectrum (ESI -) ([MH] -) C 36 H 30 N 3 OPt Calculated: 715.21; Found: 715.19.
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黄绿光发射，波长范 围在528～531nm之间。其中，Pt-0为参比O^N^C^O类黄绿光材料。如下表所示：For the Pt(II) complex of the examples, a clear yellow-green light emission was exhibited in the dichloromethane solution solution, with a wavelength ranging from 528 to 531 nm. Among them, Pt-0 is a reference O^N^C^O type yellow-green light material. As shown in the following table:
Figure PCTCN2018122965-appb-000025
Figure PCTCN2018122965-appb-000025
Figure PCTCN2018122965-appb-000026
Figure PCTCN2018122965-appb-000026
下面是本发明配合物的应用实例。The following are examples of the application of the complex of the present invention.
器件制备方式：Device preparation method:
器件的基本结构模型为：ITO/HTL-1(60nm)/EML-1:Pt(II)(40nm)/ETL-1(30nm)/LiF(1nm)/Al(80nm)。The basic structural model of the device was: ITO/HTL-1 (60 nm) / EML-1: Pt (II) (40 nm) / ETL - 1 (30 nm) / LiF (1 nm) / Al (80 nm).
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。The transparent anodized indium tin oxide (ITO, 20) (10 Ω/sq) glass substrate 10 was ultrasonically washed with acetone, ethanol, and distilled water in this order, and then treated with oxygen plasma for 5 minutes.
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.。 The ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus. In the evaporation equipment, the control system pressure is 10 -6 torr.
此后，向ITO衬底上蒸发厚度为60nm的空穴传输层(30)材料HTL-1。Thereafter, a hole transport layer (30) material HTL-1 having a thickness of 60 nm was evaporated onto the ITO substrate.
然后蒸发厚度为40nm的发光层材料(40)EML-1，其中掺杂一定质量分数的铂(II)配合物掺杂剂。A luminescent layer material (40) EML-1 having a thickness of 40 nm is then evaporated, wherein a certain mass fraction of platinum (II) complex dopant is doped.
然后蒸发厚度为30nm的电子传输层(50)材料ETL-1。Then, an electron transport layer (50) material ETL-1 having a thickness of 30 nm was evaporated.
然后蒸发厚度为1nm的LiF为电子注入层(60)。Then, LiF having a thickness of 1 nm was evaporated as an electron injecting layer (60).
最后蒸发厚度为80nm的Al作为阴极(70)并完成器件封装。Finally, Al having a thickness of 80 nm was evaporated as a cathode (70) and device encapsulation was completed.
其中，among them,
Figure PCTCN2018122965-appb-000027
Figure PCTCN2018122965-appb-000027
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Pt-0、TM-1,TM-2,TM-3,TM-4作为发光层中的掺杂剂和惨杂浓度。The structure and fabrication method of the device are identical, except that the organometallic complexes Pt-0, TM-1, TM-2, TM-3, TM-4 are sequentially used as dopants and impurity concentrations in the light-emitting layer.
器件对比结果下表所示：Device comparison results are shown in the table below:
Figure PCTCN2018122965-appb-000028
Figure PCTCN2018122965-appb-000028
在四齿铂(II)配合物掺杂浓度分别为10wt％，15wt％，20wt％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Pt-0的器件性能为参考，基于恶唑、噻唑和咪唑的四齿铂(II)配合物TM-1,TM-2,TM-3,TM-4的器件在启动电压V on相比Pt-0的器件有一定的降低，尤其是基于TM-4的器件其启动电压降至2.7V。同时，在1000cd/A条件下，基于TM-1,TM-2,TM-3,TM-4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TM-4,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，Pt-0,TM-1,TM-2,TM-3的效率提升较小甚至Pt-0,TM-1,TM-2的效率有一定程度的下降，但是TM-3和TM-4有较好的效率提升，尤其是TM-4,其电流效率由94.0cd/A提升至102.3cd/A，功率效率由78.0lm/W提升至86.5lm/W，外量子效率由21.5％提 升至25.8％。TM-4相对于Pt-0,TM-1,TM-2,TM-3在空间上有较大的位阻基团，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，因而TM-4在相同的器件上具有最好的性能。同时，TM-1,TM-2,TM-3相对于Pt-0在性能上也有不同程度的提升，说明基于恶唑、噻唑和咪唑的O^N^C^N类四齿铂(II)配合物具有较为广阔的应用前景和商业价值。 Under the conditions of doping concentration of tetradentate platinum (II) complexes of 10 wt%, 15 wt%, 20 wt%, the above ITO/HTL-1 (60 nm) / EML-1: Pt (II) (40 nm) / ETL - 1 (30 nm) / LiF (1 nm) / Al (80 nm) device basic structure preparation device. Based on the performance of Pt-0 based devices, the four-tooth platinum (II) complexes TM-1, TM-2, TM-3, TM-4 based on oxazole, thiazole and imidazole are at the startup voltage V on phase. There is a certain reduction in devices compared to Pt-0, especially for devices based on TM-4 whose startup voltage drops to 2.7V. At the same time, under 1000 cd/A conditions, devices based on TM-1, TM-2, TM-3, TM-4 have current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) relative to Pt-based. The -0 devices have different degrees of improvement, especially TM-4, which is more obvious in current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE). When the doping concentration of the tetradentate platinum (II) complex increases, the efficiency of Pt-0, TM-1, TM-2, TM-3 increases little or even Pt-0, TM-1, TM-2 efficiency A certain degree of decline, but TM-3 and TM-4 have better efficiency, especially TM-4, its current efficiency is increased from 94.0cd/A to 102.3cd/A, and the power efficiency is improved from 78.0lm/W to At 86.5 lm/W, the external quantum efficiency increased from 21.5% to 25.8%. Compared with Pt-0, TM-1, TM-2 and TM-3, TM-4 has a large sterically hindered group in space, which can effectively reduce the aggregation between molecules, avoid the formation of exciplex and improve luminescence. Efficiency, and thus TM-4 has the best performance on the same device. At the same time, TM-1, TM-2, TM-3 have different degrees of performance improvement relative to Pt-0, indicating O^N^C^N tetradentate platinum (II) based on oxazole, thiazole and imidazole. The complex has a broad application prospect and commercial value.

Claims (15)

  1. 一种基于恶唑、噻唑和咪唑的O^N^C^N四齿铂(II)配合物材料,其结构如式(1)所示：An O^N^C^N tetradentate platinum(II) complex material based on oxazole, thiazole and imidazole, the structure of which is shown in formula (1):
    Figure PCTCN2018122965-appb-100001
    Figure PCTCN2018122965-appb-100001
    其中，A 1－A 4为取代的或非取代的五元环、六元环、稠环结构；X为氧，硫或者取代的氮-NR 0，R 0为一个或多个R取代或未取代C1-C8烷基、C5-C20的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein, A 1 -A 4 is a substituted or unsubstituted five-membered ring, six-membered ring, fused ring structure; X is oxygen, sulfur or substituted nitrogen-NR 0 , and R 0 is one or more R substituted or not Substituting a C1-C8 alkyl group, a C5-C20 aryl group or a heteroaryl group, R is a halogen, a C1-C4 alkyl group, a diphenylamino group, a carbazolyl group, a fluorenyl group.
  2. 根据权利要求1所述的配合物材料，其结构如式(2)所示：The complex material according to claim 1, which has the structure shown in the formula (2):
    Figure PCTCN2018122965-appb-100002
    Figure PCTCN2018122965-appb-100002
    其中R 1－R 14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、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 14相互通过共价键连接成环；其中X 1－X 22为碳，X为氧，硫或者取代的氮-NR 0，R 0为一个或多个R取代或未取代C1-C6烷基、C5-C15的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen-NR 0 , R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroaryl, R is halogen, C1-C4 alkyl, diphenylamine Base, carbazolyl, fluorenyl.
  3. 根据权利要求2所述的配合物材料，其中R 1－R 14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 14相互通过共价键连接成环，X为氧，硫或者取代的氮-NR 0，R 0为下列取代基： The complex material according to claim 2, wherein R 1 - R 14 are independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, diarylamine, saturated alkyl having 1-10 C atoms, a 5-20 C atom-substituted or unsubstituted aryl group substituted by halogen or one or more C1-C4 alkyl groups, substituted with halogen or one or more C1-C4 alkyl groups having 5-20 C atoms Or unsubstituted heteroaryl, or adjacent R 1 -R 14 are bonded to each other by a covalent bond, X is oxygen, sulfur or substituted nitrogen -NR 0 , and R 0 is the following substituent:
    Figure PCTCN2018122965-appb-100003
    Figure PCTCN2018122965-appb-100003
    Figure PCTCN2018122965-appb-100004
    Figure PCTCN2018122965-appb-100004
  4. 根据权利要求3所述的配合物材料，其结构如下式所示：The complex material according to claim 3, which has the structure shown in the following formula:
    Figure PCTCN2018122965-appb-100005
    Figure PCTCN2018122965-appb-100005
    其中R' 1～R' 4为独立地为氢、含1－6个C原子的饱和烷基、二芳胺基、含5－10个C原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个C1－C4烷基取代的或未取代的杂芳基。 Wherein R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
  5. 根据权利要求4所述的配合物材料，其中R' 1～R' 4的4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原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个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或含1－6个C原子的饱和烷基。 The complex material according to claim 4, wherein among the four groups of R' 1 to R' 4 , 0 to 3 groups are independently represented as a diarylamine group and contain 5 to 10 C atoms. An aryl group substituted or unsubstituted with halogen or one to three C1-C4 alkyl groups, a heteroaryl group substituted by halogen or one to three C1-C4 alkyl groups having 5 to 10 C atoms, other The group independently is represented by hydrogen or a saturated alkyl group having 1 to 6 C atoms.
  6. 根据权利要求5所述的配合物材料，其中R' 2～R' 4的中的一个基团选自二苯胺基、苯、吡啶、咔唑基、异丙基或叔丁基，其它基团独立的表示为氢；R' 1表示为氢。 The complex material according to claim 5, wherein one of R' 2 to R' 4 is selected from the group consisting of diphenylamine, benzene, pyridine, carbazolyl, isopropyl or tert-butyl, and other groups Independently represented as hydrogen; R' 1 is represented as hydrogen.
  7. 根据权利要求5所述的配合物材料，R' 1～R' 4表示为氢；X为氧，硫或者取代的氮-N R 0，R 0为C1－C8的烷基。 The complex material according to claim 5, wherein R' 1 to R' 4 are represented by hydrogen; X is oxygen, sulfur or substituted nitrogen - N R 0 , and R 0 is a C1-C8 alkyl group.
  8. 根据权利要求2所述的配合物，其具有如下结构：The complex according to claim 2 having the following structure:
    Figure PCTCN2018122965-appb-100006
    Figure PCTCN2018122965-appb-100006
    Figure PCTCN2018122965-appb-100007
    Figure PCTCN2018122965-appb-100007
    Figure PCTCN2018122965-appb-100008
    Figure PCTCN2018122965-appb-100008
    Figure PCTCN2018122965-appb-100009
    Figure PCTCN2018122965-appb-100009
    Figure PCTCN2018122965-appb-100010
    Figure PCTCN2018122965-appb-100010
    Figure PCTCN2018122965-appb-100011
    Figure PCTCN2018122965-appb-100011
    Figure PCTCN2018122965-appb-100012
    Figure PCTCN2018122965-appb-100012
    Figure PCTCN2018122965-appb-100013
    Figure PCTCN2018122965-appb-100013
  9. 根据权利要求8所述的配合物，其具有如下结构：The complex according to claim 8, which has the following structure:
    Figure PCTCN2018122965-appb-100014
    Figure PCTCN2018122965-appb-100014
  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：The precursor of the complex according to any one of claims 1-9, that is, a ligand, which has the following structural formula:
    Figure PCTCN2018122965-appb-100015
    Figure PCTCN2018122965-appb-100015
    其中，A 1－A 4为取代的或非取代的五元环、六元环、稠环结构；X为氧，硫或者取代的氮-NR 0，R 0为一个或多个R取代或未取代C1-C8烷基、C5-C20的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein, A 1 -A 4 is a substituted or unsubstituted five-membered ring, six-membered ring, fused ring structure; X is oxygen, sulfur or substituted nitrogen-NR 0 , and R 0 is one or more R substituted or not Substituting a C1-C8 alkyl group, a C5-C20 aryl group or a heteroaryl group, R is a halogen, a C1-C4 alkyl group, a diphenylamino group, a carbazolyl group, a fluorenyl group.
  11. 权利要求10所述的前体，其结构式如下：The precursor of claim 10 having the following structural formula:
    Figure PCTCN2018122965-appb-100016
    Figure PCTCN2018122965-appb-100016
    其中R 1－R 14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、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 14相互通过共价键连接成环；其中X 1－X 22为碳，X为氧，硫或者取代的氮(-NR 0)，R 0为一个或多个R取代或未取代C1-C6烷基、C5-C15的芳基或杂芳基，R为卤素，C1-C4烷基，二苯胺基、咔唑基、芴基。 Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, hydrazine, sulfur, halogen, hydroxy, acyl, alkoxy, acyloxy, amino, nitro, acylamino, cyano, carboxy, styryl, aminocarbonyl, Carboyl, benzylcarbonyl, aryloxy, saturated alkyl having 1 to 30 C atoms, unsaturated alkyl having 1 to 20 C atoms, substituted or unsubstituted with 5 to 30 C atoms An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 C atoms, or an adjacent R 1 to R 14 are bonded to each other by a covalent bond; wherein X 1 -X 22 is carbon and X is oxygen, Sulfur or substituted nitrogen (-NR 0 ), R 0 is one or more R substituted or unsubstituted C1-C6 alkyl, C5-C15 aryl or heteroaryl, R is halogen, C1-C4 alkyl, Diphenylamino, carbazolyl, fluorenyl.
  12. 权利要求11所述的前体，其结构式如下：The precursor of claim 11 having the following structural formula:
    Figure PCTCN2018122965-appb-100017
    Figure PCTCN2018122965-appb-100017
    其中R' 1～R' 4为独立地为氢、含1－6个C原子的饱和烷基、二芳胺基、含5－10个C原子被卤素或一至三个C1－C4烷基取代的或未取代的芳基、含5－10个C原子的被卤素或一至三个C1－C4烷基取代的或未取代的杂芳基。 Wherein R' 1 to R' 4 are independently hydrogen, a saturated alkyl group having 1 to 6 C atoms, a diarylamine group, and 5 to 10 C atoms are substituted by halogen or one to three C1-C4 alkyl groups. Or an unsubstituted aryl group, a heteroaryl group substituted with 5-10 C atoms by halogen or one to three C1-C4 alkyl groups or unsubstituted.
  13. 权利要求4所述配合物材料的制备方法：其中X＝O,S，底物A1与芳香醛A2反应得到底物A3，A3继续反应得到相应的频哪醇酯A4，A4与A5经Suzuki反应得到相应的底物A6，A6经脱甲基反应后得到配体A7，A7与K 2PtCl 4反应即得到相应的目标产物A， The method for preparing a complex material according to claim 4, wherein X = O, S, substrate A1 is reacted with aromatic aldehyde A2 to obtain substrate A3, and A3 is further reacted to obtain corresponding pinacol ester A4, and A4 and A5 are subjected to Suzuki reaction. Obtaining the corresponding substrate A6, A6 is demethylated to obtain ligand A7, and A7 reacts with K 2 PtCl 4 to obtain the corresponding target product A.
    Figure PCTCN2018122965-appb-100018
    Figure PCTCN2018122965-appb-100018
    或者；X＝NR 0，邻苯二铵B1与芳香醛B2反应得到B3,B3在碱性条件下与卤代物反应得到B4，B4进一步反应得到相应的频哪醇酯B5，B5与B6经Suzuki反应得到底物B7，B7经脱甲基后得到配体B8，B8与K 2PtCl 4反应即得到相应的目标产物B， Or; X=NR 0 , o-diphenylammonium B1 reacts with aromatic aldehyde B2 to obtain B3, B3 reacts with halogenated substance under basic conditions to obtain B4, and B4 further reacts to obtain corresponding pinacol ester B5, B5 and B6 via Suzuki The reaction gives the substrate B7, and the B7 is demethylated to obtain the ligand B8, and the B8 reacts with the K 2 PtCl 4 to obtain the corresponding target product B.
    Figure PCTCN2018122965-appb-100019
    Figure PCTCN2018122965-appb-100019
  14. 权利要求1－9任一配合物材料在OLED发光器件中的应用。Use of the complex material of any of claims 1-9 in an OLED light emitting device.
  15. 根据权利要求14所述的应用，所述权利要求1－9任一配合物材料通过热沉积、旋涂、喷墨打印以层形式施加在该器件中。The use according to claim 14, wherein the complex material of any of claims 1-9 is applied in the device in layers by thermal deposition, spin coating, ink jet printing.
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