WO2022088873A1 - 一种金属络合物及其应用 - Google Patents
一种金属络合物及其应用 Download PDFInfo
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- WO2022088873A1 WO2022088873A1 PCT/CN2021/113932 CN2021113932W WO2022088873A1 WO 2022088873 A1 WO2022088873 A1 WO 2022088873A1 CN 2021113932 W CN2021113932 W CN 2021113932W WO 2022088873 A1 WO2022088873 A1 WO 2022088873A1
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- compound
- metal complex
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 25
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- 229910052805 deuterium Inorganic materials 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 14
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
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- 125000005104 aryl silyl group Chemical group 0.000 claims description 6
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Definitions
- the present invention relates to the technical field of organic electroluminescence, in particular to the technical field of organic electroluminescence devices, and in particular to a metal complex and its application in organic electroluminescence devices.
- OLEDs organic electroluminescent devices
- OLED devices the basic structure of OLED devices is that various organic functional material films with different functions are mixed between metal electrodes, like a sandwich structure. Driven by current, holes and electrons are injected from the cathode and anode, and holes and electrons are respectively injected. After moving a certain distance, the light-emitting layer is recombined and released in the form of light or heat, thereby producing the luminescence of the OLED.
- organic functional materials are the core components of organic electroluminescent devices, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. A major factor in device performance.
- organic functional materials include fluorescent materials and phosphorescent materials.
- the fluorescent material is usually an organic small molecule material, and generally can only use 25% of the singlet state to emit light, so the luminous efficiency is relatively low.
- the phosphorescent material can utilize the energy of 75% triplet excitons in addition to the 25% singlet state due to the spin-orbit coupling effect caused by the heavy atom effect, so the luminous efficiency can be improved.
- phosphorescent materials started late, and the thermal stability, lifespan, and color saturation of the materials need to be improved, which is a challenging topic.
- various organometallic compounds have been developed as such phosphorescent materials.
- the market still expects the development of novel materials that can further improve the performance of organic electroluminescent devices.
- the present invention provides high-performance organic electroluminescent devices and novel materials capable of realizing such organic electroluminescent devices.
- the present inventors have repeatedly conducted intensive studies in order to achieve the aforementioned object, and found that a high-performance organic electroluminescence device can be obtained by using a metal complex including a structure represented by the following formula (1) as a ligand.
- One of the objectives of the present invention is to provide a metal complex, which has the advantages of low sublimation temperature, high optical and electrochemical stability, high color saturation, high luminous efficiency, long device life and the like, Can be used in organic electroluminescent devices. Especially as a green light-emitting dopant, it has the possibility of being applied to the OLED industry.
- R1-R18 is the structure shown in formula (2);
- M is independent of Pt, Pd;
- X independently represents O, S, Se, CRaRb;
- L1-L3 are each independently selected from direct bonding single bond, O, S, Se, NRc, CRdRe, SO, SO2, PO(Rf)(Rg);
- L4 is a single bond, O, substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C3-C30 cycloalkylene, substituted or unsubstituted C1-C20 heteroalkylene, substituted or unsubstituted C7-C30 aralkylene, substituted or unsubstituted C2-C20 alkenylene, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 alkene
- Aryl substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C3-C30 arylenesilyl, substituted or unsubstituted C0-C20 imino;
- R1-R18, R101-R102 and Ra-Rg are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or Unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, Substituted or unsubstituted C3-C30 arylsilyl group, substituted or unsubstituted
- substitution numbers of R101 and R102 independently represent no substitution to the maximum substitution number.
- R1-R18 is the structure shown in formula (2);
- X independently represents O, S, Se, CRaRb;
- L4 is a single bond, O, substituted or unsubstituted C1-C10 alkylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C2-C10 heteroalkylene, substituted or unsubstituted C7-C20 aralkylene, substituted or unsubstituted C2-C20 alkenylene, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 alkene Aryl, substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C3-C30 arylenesilyl, substituted or unsubstituted C0-C20 imino;
- R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra and Rb are as defined above.
- L4 is a single bond, O and one of the following structures:
- Rx represents no substitution to the maximum number of substitutions.
- Rx is multi-substituted, two adjacent substituents can be connected to each other to form a cyclic or combined ring structure;
- Rx and Ry are independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, Substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl , substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 aryl Silyl group, substituted or unsubstituted C0-C20 amine group, cyano group,
- R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx and Ry are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, Substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C7-C10 aralkyl, substituted or unsubstituted C2-C20 alkenyl , substituted or unsubstituted C3-C8 alkylsilyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, substituted or unsubstituted C3-C10 aryl Silyl group, substituted or unsubstituted C0-C6 amine group, cyano group.
- R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx and Ry are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, Substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted phenylalkyl, substituted or unsubstituted C6-C10 aryl, substituted substituted or unsubstituted C3-C10 heteroaryl.
- R18 is deuterium, substituted or unsubstituted straight-chain carbon atom C1-C4 alkyl, substituted or unsubstituted C1-C6 cycloalkyl, and the substitution is substituted by deuterium and halogen.
- the precursor of the metal complex has the following structure:
- R1-R18 is the structure shown in formula (2);
- R1-R18, R101, and R102 are the same as those described above.
- Another object of the present invention is to provide an electroluminescent device comprising: a cathode, an anode and an organic layer disposed between the cathode and the anode, at least one layer of the organic layer contains a metal complex.
- Another object of the present invention is to provide an electroluminescent device, wherein the organic layer comprises a light-emitting layer, and the metal complex is used as a material in the light-emitting layer, especially as a green light-emitting material;
- Another object of the present invention is to provide an electroluminescent device, wherein the organic layer includes a hole injection layer, and the metal complex is used as a material in the hole injection layer.
- the device results show that the compound of the present invention has the advantages of high optical and electrochemical stability, high color saturation, high luminous efficiency, long device life and the like, and can be used in organic electroluminescent devices. Especially as a green phosphorescent material, it has the possibility of being applied to the OLED industry.
- A1-3 (96g, 0.63mol, 1.0eq), benzaldehyde (74.6g, 0.7mol, 1.1eq), potassium hydroxide (179.3g, 3.2mol, 4.0eq), deionized water were sequentially added to a 3L three-necked flask (195ml), methanol (670ml), replaced by vacuum and nitrogen three times, heated to 50°C and reacted overnight. A large amount of solid was precipitated in the reaction, cooled to room temperature, filtered, collected and added to ethyl acetate (500 ml), stirred to dissolve, and washed twice with 200 ml of deionized water each time.
- A1-4 (80g, 0.33mol, 1.0eq), A1-2 (135.6g, 0.33mol, 1.0eq), ammonium acetate (155.2g, 2.0mol, 6.0eq), acetic acid (350ml) were sequentially added to a 1L three-necked flask ), replaced by vacuum and nitrogen three times, heated to reflux and reacted overnight. The mixture was cooled to room temperature, concentrated to remove acetic acid, and the spin-dried solid was added with dichloromethane (1.0 L), stirred to dissolve, and deionized water was added for washing twice with 300 ml each.
- reaction solution was added to a beaker containing deionized water (650 ml), stirred to precipitate a solid, and the solid was collected by filtration.
- Sublimation pure A 1 (3.64 g, yield 69.5%) was obtained after sublimation purification of 5.23 g of A 1 crude product, mass spectrum: 774.2 (M+H).
- the orange-yellow compound A 82 (3.97 g, yield 63.7%) can be obtained only by changing the corresponding raw materials.
- Sublimation pure A 82 (2.58 g, yield 64.9%) was obtained after sublimation purification of 3.97 g of crude A 82.
- the orange-yellow compound A 89 (3.57 g, yield 56.7%) can be obtained only by changing the corresponding raw materials.
- Sublimation pure A 89 (2.16 g, yield 60.5%) was obtained after sublimation purification of 3.57 g of crude A89.
- the orange-yellow compound A 100 (4.12 g, yield 58.8%) can be obtained only by changing the corresponding raw materials.
- Sublimation pure A 100 (2.59 g, yield 62.86%) was obtained after sublimation purification of 4.12 g of crude A 100.
- the orange-yellow compound A 125 (3.93 g, yield 59.3%) can be obtained only by changing the corresponding raw materials.
- Sublimation pure A 125 (2.28 g, yield 58.0%) was obtained after sublimation purification of 3.93 g of crude A 125.
- the orange-yellow compound A 197 (3.67 g, yield 55.8%) can be obtained only by changing the corresponding raw materials.
- Sublimation pure A 197 (2.08 g, yield 56.6%) was obtained after sublimation purification of 3.67 g of crude A 197. Mass spectrum: 903.9 (M+H).
- a 50mm*50mm*1.0mm glass substrate with ITO (100nm) transparent electrodes was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees, and then treated with N2Plasma for 30 minutes.
- the washed glass substrate was mounted on the substrate holder of the vacuum evaporation device, and the compound HATCN was evaporated on the surface of the transparent electrode line side in a manner to cover the transparent electrode to form a thin film with a thickness of 5 nm, and then evaporated.
- ETL film layer (25nm) LiQ film layer (1nm) was evaporated on the light-emitting layer in turn, and finally a layer of metal Al (100nm) was evaporated as an electrode.
- Example 12 A 197 4.69 54 534 191 Comparative Example 1 Contrast 1 4.84 31 510 115 Comparative Example 2 Contrast 2 4.86 38 517 136
- the organic electroluminescence device using the compound of the present invention as the green light dopant shows more superior performance in driving voltage, luminous efficiency and device life compared with the comparative compound.
- the compound of the present invention has the advantages of high light and electrochemical stability, high color saturation, high luminous efficiency, long device life and the like, and can be used in organic electroluminescent devices. Especially as a green phosphorescent material, it has the possibility of being applied to the OLED industry.
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Abstract
涉及一种金属络合物及其应用。所述金属络合物具有式(1)所示结构。所述金属络合物具有光、电、热稳定性好,发光效率高,寿命长,色饱和度高等优点,可用于有机发光器件中,特别是作为绿色发光磷光材料,具有应用于AMOLED产业的可能。
Description
本发明涉及有机电致发光技术领域,尤其涉及有机电致发光器件技术领域,特别涉及一种金属络合物及其在有机电致发光器件上的应用。
目前,作为新一代显示技术的有机电致发光器件(OLED)在显示和照明技术方面都获得了越来越多的关注,应用前景十分广泛。但是,和市场应用要求相比,OLED器件的发光效率、驱动电压、使用寿命等性能还需要继续加强和改进。
一般来说,OLED器件基本结构为在金属电极中间夹杂各种不同功能的有机功能材料薄膜,犹如一个三明治的结构,在电流的驱动下,从阴阳两极分别注入空穴和电子,空穴和电子在移动一段距离后,在发光层得到复合,并以光或热的形式进行释放,从而产生了OLED的发光。然而,有机功能材料是有机电致发光器件的核心组成部分,材料的热稳定性、光化学稳定性、电化学稳定性、量子产率、成膜稳定性、结晶性、色饱和度等都是影响器件性能表现的主要因素。
一般地,有机功能材料包括荧光材料和磷光材料。荧光材料通常为有机小分子材料,一般只能利用25%单重态发光,所以发光效率比较低。而磷光材料由于重原子效应引起地自旋轨道耦合作用,除了利用25%单重态之外,还可以利用75%三重态激子的能量,所以发光效率可以得到提升。但是相较于荧光材料,磷光材料起步较晚,且材料的热稳定性、寿命、色饱和度等都有待提升,是一个具有挑战性的课题。现有技术中,已经有人开发出各种有机金属化合物作为这种磷光材料。然而,市场仍然期望能进一步改善有机电致发光器件性能的新型材料的开发。
发明内容
本发明提供高性能的有机电致发光器件及可实现这样的有机电致发光器件的新型材料。
本发明人为了达成前述目的而反复进行了深入的研究,结果发现,通过使用包含下述式(1)表示的结构作为配体的金属络合物,可以得到高性能的有机电致发光器件。
本发明的目的之一在于提供一种金属络合物,该类金属络合物具有升华温度较低,光、电化学稳定性高,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为绿色发光掺杂体,具有应用于OLED产业的可能。
一种金属络合物,其具有式(1)所示的结构:
其中R1-R18至少之一为式(2)所示的结构;
其中
*表示与式(1)连接的位置;
M独立的为Pt、Pd;
X独立的表示O,S,Se,CRaRb;
L1-L3各自独立的选自直接键合单键,O,S,Se,NRc,CRdRe,SO,SO2,PO(Rf)(Rg);
L4为单键,O,取代的或未取代的C1-C20亚烷基、取代的或未取代的C3-C30亚环烷基、取代的或未取代的C1-C20亚杂烷基、取代的或未取代的C7-C30亚芳烷基,取代或未取代的C2-C20的亚烯基、取代的或未取代的C3-C30亚烷基硅基、取代的或未取代的C6-C30亚芳基、取代的或未取代的C3-C30亚杂芳基、取代的或未取代的C3-C30亚芳基硅基、取代或未取代的C0-C20的亚胺基;
其余R1-R18、R101-R102和Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C20烷基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C20杂烷基、取代的或未取代的C7-C30芳烷基、取代的或未取代的C1-C20烷氧基、取代的或未取代的C6-C30芳氧基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C30烷基硅基、取代的或未取代的C6-C30芳基、取代的或未取代的C3-C30杂芳基、取代的或未取代的C3-C30芳基硅基、取代或未取代的C0-C20的胺基、氰基、腈、异腈、膦基;或者任意两个相邻的基团之间相互连接以形成环状结构或者并环结构;所述取代为被氘、卤素、C1-C4烷基、氰基所取代;
R101、R102的取代个数独立的表示无取代到最大取代个数。
优选:其具有式(3)所示的结构:
其中R1-R18至少之一为式(2)所示的结构;
其中*,X,L4,R1-R18,R101-R102和Ra-Rb与前述定义相同。
优选:其具有式(4)所示的结构:
其中
X独立的表示O,S,Se,CRaRb;
L4为单键,O,取代的或未取代的C1-C10亚烷基、取代的或未取代的C3-C10亚环烷基、取代的或未取代的C2-C10亚杂烷基、取代的或未取代的C7-C20亚芳烷基,取代或未取代的C2-C20的亚烯基、取代的或未取代的C3-C30亚烷基硅基、取代的或未取代的C6-C30亚芳基、取代的或未取代的C3-C30亚杂芳基、取代的或未取代的C3-C30亚芳基硅基、取代或未取代的C0-C20的亚胺基;
R1、R2、R7、R8、R10、R11、R18、R101、R102、Ra和Rb与前述定义相同。
优选:其中L4为单键、O及以下结构之一:
其中
*表示与式(1)及式(2)连接的位置
Rx的个数表示无取代到最大取代个数,当Rx为多取代时,相邻的两个取代基可以互相连接以形成环状或并环结构;
Rx和Ry独立地为氢、氘、卤素、取代的或未取代的C1-C20烷基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C20杂烷基、取代的或未取代的C7-C30芳烷基、取代的或未取代的C1-C20烷氧基、取代的或未取代的C6-C30芳氧基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C30烷基硅基、取代的或未取代的C6-C30芳基、取代的或未取代的C3-C30杂芳基、取代的或未取代的C3-C30芳基硅基、取代或未取代的C0-C20的胺基、氰基、腈、异腈、膦基。
优选:其中R1、R2、R7、R8、R10、R11、R18、R101、R102、Ra、Rb、Rx和Ry独立地选自氢、氘、卤素、取代的或未取代的C1-C8烷基、取代的或未取代的C3-C10环烷基、取代的或未取代的C1-C8杂烷基、取代的或未取代的C7-C10芳烷基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C8烷基硅基、取代的或未取代的C6-C10芳基、取代的或未取代的C3-C10杂芳基、取代的或未取代的C3-C10芳基硅基、取代或未取代的C0-C6的胺基、氰基。
优选:其中R1、R2、R7、R8、R10、R11、R18、R101、R102、Ra、Rb、Rx和Ry独立地选自氢、氘、卤素、取代的或未取代的C1-C8烷基、取代的或未取代的C3-C10环烷基、取代的或未取代的C1-C8杂烷基、取代的或未取代的苯基烷基、取代的或未取代的C6-C10芳基、取代的或未取代的C3-C10杂芳基。
优选:其中R18为氘、取代或未取代的直链碳原子C1-C4烷基、取代或未取代的C1-C6个环烷基,所述取代为被氘、卤素所取代。
优选:其中R1和R2至少之一不为氢。
作为优选的金属络合物,其中优选为以下结构式之一;
金属络合物的前体,具有如下结构:
其中R1-R18至少之一为式(2)所示的结构;
其中R1-R18、R101、R102的定义与前述相同。
本发明的目的之一还在于提供一种电致发光器件,其包括:阴极,阳极以及设置在阴极阳极之间的有机层,所述有机层至少一层包含金属络合物。
本发明的另一目的在于提供一种电致发光器件,其中所述有机层包含发光层,所述金属络合物作为发光层中材料,特别是作为绿色发光材料;
本发明的另一目的还在于提供一种电致发光器件,其中所述有机层包含空穴注入层,所述金属络合物作为空穴注入层中材料。
器件结果表明本发明的化合物具有光、电化学稳定性高,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为绿色磷光材料,具有应用于OLED产业的可能。
图1化合物A 39的HNMR谱图,
图2化合物A 82的HNMR谱图,
图3化合物A 39的UV/PL谱图,
图4化合物A 82的UV/PL谱图。
所述实施例仅仅是为了便于理解技术发明,不应视为本发明的具体限制。
本发明中的化合物合成中涉及的原物料和溶剂等均购自于Alfa、Acros等本领域技术人员熟知的供应商。
实施例1 化合物A1的合成
中间体A1-6的合成
化合物A1-2的合成
向1L单口烧瓶中依次加入A1-1(120g,0.6mol,1.0eq),碘单质(168.3g,0.6mol,1.0eq),吡啶(600ml),真空、氮气置换三次,升温至回流反应过夜。反应有大量固体析出, 降至室温,过滤,滤饼用甲醇淋洗两次,共计200ml,抽干后固体再用甲醇热打浆2次,每次200ml。收集固体,干燥得到类白色固体A1-2(207.3g,收率85.1%)。质谱:405.0(M+H)化合物A1-4的合成
向3L三口烧瓶中依次加入A1-3(96g,0.63mol,1.0eq),苯甲醛(74.6g,0.7mol,1.1eq),氢氧化钾(179.3g,3.2mol,4.0eq),去离子水(195ml),甲醇(670ml),真空、氮气置换三次,升温至50℃反应过夜。反应有大量固体析出,降至室温,过滤,收集固体加到乙酸乙酯(500ml)中,搅拌溶清,加入去离子水进行水洗两次,每次200ml。有机相浓缩至剩余少量,加入甲醇(250ml)进行打浆纯化,抽滤,收集滤饼干燥得到白色固体A1-4(93.5g,收率61.4%)。质谱:239.2(M+H)
化合物A1-5的合成
向1L三口烧瓶中依次加入A1-4(80g,0.33mol,1.0eq),A1-2(135.6g,0.33mol,1.0eq),乙酸铵(155.2g,2.0mol,6.0eq),乙酸(350ml),真空、氮气置换三次,升温至回流反应过夜。降至室温,浓缩除去乙酸,旋干的固体加入二氯甲烷(1.0L),搅拌溶清,加入去离子水进行水洗两次,每次300ml。有机相浓缩至剩余少量,加入甲醇(250ml)进行结晶纯化,抽滤,收集固体再用甲醇(300ml)热打浆2次。干燥得到白色固体A1-5(119.6g,收率85.6%)。质谱:417.3(M+H)
化合物A1-6的合成
向一个1L单口瓶,依次将化合物A1-5(110.0g,0.260mol,1.0eq)、联硼酸频那醇酯(80.5g,0.31mol,1.2eq),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(3.87g,5.28mmol,0.02eq)、醋酸钾(51.8g,0.52mol,2.0eq),二氧六环(900ml),氮气置换三次后加热至100℃,保温搅拌6h,TLC监控(展开剂:乙酸乙酯/正己烷=1/10),原料A1-5基本反应完全。反应液降温至40℃,进行硅藻土过滤,用少量二氧六环冲洗滤饼,滤液减压浓缩至200ml,加入甲醇(400ml)室温下搅拌2h,过滤,得到固体采用四氢呋喃/甲醇(100ml/200ml)重结晶两次,过滤烘干得到米白色固体化合物A1-6(84.1g,收率68.7%)。质谱:464.3(M+H).
化合物A 1的合成
化合物A1-7的合成
向一个3L三口瓶,依次将化合物A1-6(75.0g,0.16mol,1.0eq)、2,4-二氯-6-甲基吡啶(39.3g,0.24mol,1.5eq),四(三苯基膦)钯(9.35g,8.09mmol,0.05eq)、氢氧化钠(51.8g,0.52mol,3.0eq),二氧六环(650ml),去离子水(130ml),氮气置换三次后加热至70℃,保温搅拌6h,TLC监控(展开剂:二氯甲烷/正己烷=1/10),原料A1-6基本反应完全。反应液降温至室温,往体系加入二氯甲烷(300mL)和去离子水(300mL),萃取,收集有机相过硅胶,再用二氯甲烷(200mL)冲洗硅胶,滤液旋干得到的固体加入甲苯(150ml)/甲醇(350ml)重结晶3次,烘干得到白色固体化合物A1-7(54.1g,收率72.3%)。质谱:464.0(M+H).
化合物A1-8的合成
向一个1L三口瓶,依次将化合物A1-7(10.5g,22.6mmol,1.0eq)、二苯并呋喃-4-硼酸(7.2g,34.0mmol,1.5eq),二氯-二叔丁基-(4-二甲基氨基苯基)磷钯(II)(0.24g,0.34mmol,0.015eq)、磷酸三钾(9.63g,45.3mmol,2.0eq),二氧六环(300ml),去离子水(100ml),氮气置换三次后加热至60℃,保温搅拌3h,TLC监控(展开剂:乙酸乙酯/正己烷=1/20),原料A1-7基本反应完全。反应液降温至室温,往体系加入二氯甲烷(200mL)和去离子水(100mL),萃取,收集有机相旋干,进行柱层析纯化(洗脱剂:乙酸乙酯/正己烷=1/40),干燥得到白色固体化合物A1-8(10.6g,收率79.1%)。质谱:595.7(M+H).
化合物A1-9的合成
将A1-8(10.6g,17.8mmol,1.0eq),吡啶盐酸盐(98.8g,0.85mol,48eq)、加入到500mL单口瓶中,再加入二氯苯(24ml),搅拌,氮气置换三次,升温至190℃,反应2.5h后TLC监测(展开剂:乙酸乙酯/正己烷=1/3),原料反应完全,反应降至室温。向反应中加入饱和碳酸氢钠溶液(120ml)和甲苯(120ml),搅拌溶清分液,有机相再水洗2次(150ml/次),收集有机相旋干。粗品硅胶柱层析纯化(洗脱剂:乙酸乙酯/正己烷=1/20),干燥得到黄色固体A1-9(8.33g,收率80.5%)。质谱:581.2(M+H)。
化合物A 1的合成
取1L单口瓶,投入A1-9(6.5g,11.19mmol,1.0eq),氯亚铂酸钾(8.11g,17.35mmol,1.55eq)和四丁基溴化铵(541mg,1.68mmol,0.15eq)和乙酸(650ml)。真空、 氮气置换三次,在氮气保护下加热至125℃,反应72h。TLC监测(展开剂:二氯甲烷/正己烷=1/2),原料A1-9反应完全,反应降至室温。反应液加到装有去离子水(650ml)的烧杯中,搅拌析出固体,过滤收集固体。粗品进行硅胶柱层析分离(洗脱剂:二氯甲烷/正己烷=1/8),所得橙黄色固体,再采用二氯甲烷(60ml)/甲醇(80ml)重结晶1次,得到橙黄色化合物A1(5.23g,收率60.3%)。将5.23克A 1粗品升华纯化后得到升华纯A 1(3.64g,收率69.5%),质谱:774.2(M+H)。
1H NMR(400MHz,CDCl
3)δ8.65(s,1H),8.44(s,1H),8.23(d,J=30.0Hz,4H),8.12–7.94(m,3H),7.72(d,J=25.0Hz,3H),7.58–7.22(m,10H),6.97(s,1H),3.27(s,3H).
实施例2 化合物A 3的合成
化合物A3-2的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:671.8(M+H)。
化合物A3-3的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:657.8(M+H)。
化合物A 3的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 3(4.66g,收率59.4%)。将4.66克A 3粗品升华纯化后得到升华纯A 3(2.91g, 收率61.4%)。质谱:850.8(M+H)。
1H NMR(400MHz,CDCl
3)δ8.64(s,1H),8.42(s,1H),8.24(d,J=30.0Hz,4H),8.05(d,J=30.0Hz,4H),7.72(d,J=25.0Hz,3H),7.59–7.34(m,11H),7.29(d,J=5.0Hz,2H),6.98(s,1H),3.28(s,3H).
实施例3 化合物A 28的合成
中间体A 28-4的合成
化合物A28-2的合成
参照化合物A1-4的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:257.3(M+H)。
化合物A28-3的合成
参照化合物A1-5的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:435.3(M+H)。
化合物A28-4的合成
参照化合物A1-5的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:482.4(M+H)。
化合物A 28的合成
化合物A28-5的合成
参照化合物A1-7的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:482.0(M+H)。
化合物A28-6的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:595.7(M+H)。
化合物A28-9的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:599.7(M+H)。
化合物A 28的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可,同时采用氘代乙酸做为反应溶剂,得到橙黄色化合物A 28(4.24g,收率64.1%)。将4.24克A 28粗品升华纯化后得到升华纯A 28(2.64g,收率62.2%)。质谱:871.8(M+H)。
1H NMR(400MHz,CDCl
3)δ8.43(d,J=10.0Hz,2H),8.23(d,J=30.0Hz,4H),8.05(d,J=30.0Hz,4H),7.72(d,J=25.0Hz,3H),7.57–7.34(m,11H),7.09(d,J=35.0Hz,2H).实施例4化合物A 39的合成
中间体A 39-3的合成
化合物A39-1的合成
参照化合物A1-4的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:257.3(M+H)。
化合物A39-2的合成
参照化合物A1-5的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:435.3(M+H)。
化合物A39-3的合成
参照化合物A1-5的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:482.4(M+H)。
化合物A 39的合成
化合物A39-4的合成
参照化合物A1-7的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:576.2(M+H)。
化合物A39-5的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:784.0(M+H)。
化合物A39-6的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:770.0(M+H)。
化合物A 39的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可,同时采用氘代乙酸做为反应溶剂,得到橙黄色化合物A 39(4.37g,收率67.4%)。将4.37克A 39粗品升华纯化后得到升华纯A 39(2.66g,收率60.8%)。质谱:963.0(M+H)。
1H NMR(400MHz,CDCl
3)δ8.22(d,J=15.9Hz,2H),7.98(dt,J=15.0,7.3Hz,5H),7.84–7.65(m,5H),7.64–7.31(m,11H),7.18(t,J=7.8Hz,1H),6.69(t,1H),3.28(s,3H),1.52(d,J=44.0Hz,18H).
实施例5 化合物A 71的合成
化合物A71-2的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:687.9(M+H)。
化合物A71-3的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:672.8(M+H)。
化合物A 71的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 71(4.37g,收率56.2%)。将4.37克A 71粗品升华纯化后得到升华纯A 71(2.4g,收率54.9%)。质谱:866.9(M+H)。H NMR(400MHz,CDCl
3)δ8.63(s,1H),8.53(s,2H),8.41(s,1H),8.37–8.17(m,6H),7.72(d,J=25.0Hz,3H),7.55–7.37(m,11H),7.29(d,J=5.0Hz,2H),7.01(s,1H),3.28(s,3H).
实施例6 化合物A 82的合成
化合物A82-1的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:724.0(M+H)。
化合物A82-2的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:710.0(M+H)。
化合物A 82的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 82(3.97g,收率63.7%)。将3.97克A 82粗品升华纯化后得到升华纯A 82(2.58g, 收率64.9%)。质谱:903.0(M+H)。
1H NMR(400MHz,CDCl
3)δ8.22(s,1H),8.18(d,J=5.9Hz,2H),7.98(d,J=7.7Hz,1H),7.88(s,1H),7.85–7.78(m,1H),7.71–7.41(m,10H),7.39–7.32(m,1H),7.31–7.23(m,2H),7.19(t,J=7.6Hz,1H),6.67(t,J=6.8Hz,1H),3.27(s,3H),1.59(s,18H).
实施例7 化合物A 89的合成
化合物A89-2的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:645.8(M+H)。
化合物A89-3的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:631.7(M+H)。
化合物A 89的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 89(3.57g,收率56.7%)。将3.57克A 89粗品升华纯化后得到升华纯A 89(2.16g,收率60.5%)。质谱:824.8(M+H)。
1H NMR(400MHz,CDCl
3)δ8.66(s,1H),8.45(s,1H),8.24(d,J=30.0Hz,4H),8.13–7.95(m,3H),7.73(d,J=25.0Hz,3H),7.58–7.22(m,10H),6.99(s,1H),3.28(s,3H).
实施例8 化合物A 100的合成
化合物A100-2的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:858.1(M+H)。
化合物A100-3的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:844.1(M+H)。
化合物A 100的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 100(4.12g,收率58.8%)。将4.12克A 100粗品升华纯化后得到升华纯A 100(2.59g,收率62.86%)。质谱:1037.2(M+H)。
1H NMR(400MHz,CDCl
3)δ8.66(s,1H),8.44(s,1H),8.22(d,J=30.0Hz,4H),8.11(s,1H),7.90(s,1H),7.83–7.66(m,4H),7.54–7.38(m,4H),7.37–7.14(m,10H),7.10(s,4H),6.99(s,1H),3.28(s,3H),1.60(s,18H).
实施例9 化合物A 111的合成
化合物A111-1的合成
参照化合物A1-6的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:555.5(M+H)。
化合物A111-2的合成
向一个500ml三口瓶,依次将化合物A111-1(11.5g,20.7mmol,1.0eq)、2,5-二溴呋喃(7.03g,31.1mmol,1.5eq),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(0.3g,0.41mmol,0.02eq)、碳酸钾(5.73g,41.8mmol,2.0eq),甲苯(115ml),乙醇(25ml),去离子水(25ml),氮气置换三次后加热至65℃,保温搅拌6h,TLC监控(展开剂:二氯甲烷/正己烷=1/15),原料A111-1基本反应完全。反应液降温至室温,往体系加入二氯甲烷(150mL)和去离子水(100mL),萃取,收集有机相旋干。粗品进行硅胶柱层析分离(洗脱剂:二氯甲烷/正己烷=1/40),所得橙类白色固体A111-2(7.46g,收率62.7%)。质谱:574.5(M+H).
化合物A111-4的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:745.9(M+H)。
化合物A111-5的合成
参照化合物A1-9的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:731.7(M+H)。
化合物A 111的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 111(3.75g,收率61.1%)。将3.75克A 111粗品升华纯化后得到升华纯A 111(2.17g,收率57.8%)。质谱:916.9(M+H)。
1H NMR(400MHz,CDCl
3)δ8.65(s,1H),8.32 –8.17(m,5H),8.05(d,J=30.0Hz,2H),7.81–7.66(m,5H),7.62–7.37(m,11H),7.29(d,J=5.0Hz,2H),7.05(s,2H),6.99(s,1H),3.28(s,3H)
实施例10 化合物A 125的合成
化合物A125-2的合成
参照化合物A111-2的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:624.5(M+H)。
化合物A125-3的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:711.8(M+H)。
化合物A125-4的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:697.8(M+H)。
化合物A 125的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 125(3.93g,收率59.3%)。将3.93克A 125粗品升华纯化后得到升华纯A 125(2.28g,收率58.0%)。质谱:890.9(M+H)。
1H NMR(400MHz,CDCl
3)δ8.64(s,1H),8.32–8.17(m,5H),7.98(s,2H),7.81–7.67(m,6H),7.61–7.45(m,5H),7.46–7.24(m,8H),6.98(s,1H),3.27(s,3H).
实施例11 化合物A 168的合成
化合物A168-1的合成
参照化合物A111-2的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:590.5(M+H)。
化合物A168-2的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:826.0(M+H)。
化合物A168-3的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:811.0(M+H)。
化合物A 168的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 168(4.22g,收率63.1%)。将4.22克A 168粗品升华纯化后得到升华纯A 168(2.69g,收率63.7%)。质谱:1005.1(M+H)。
1H NMR(400MHz,CDCl
3)δ8.66(s,1H),8.31–8.18(m,5H),8.09(s,1H),7.90(d,J=5.0Hz,6H),7.82–7.65(m,5H),7.54–7.18(m,14H),6.99(s,1H),3.28(s,3H),
实施例12 化合物A 197的合成
化合物A197-2的合成
参照化合物A111-2的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:637.6(M+H)。
化合物A197-3的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:724.9(M+H)。
化合物A197-4的合成
参照化合物A1-8的合成过程及后处理纯化方法,只需要将对应的原物料变更即可。质谱:710.8(M+H)。
化合物A 197的合成
参照化合物A 1的合成过程及后处理纯化方法,只需要将对应的原物料变更即可得到橙黄色化合物A 197(3.67g,收率55.8%)。将3.67克A 197粗品升华纯化后得到升华纯A 197(2.08g,收率56.6%)。质谱:903.9(M+H)。H NMR(400MHz,CDCl
3)δ8.67(s,1H),8.33–8.17(m,5H),7.98(s,1H),7.75(dd,J=30.0,15.0Hz,6H),7.61–7.23(m,12H),7.01(d,J=45.0Hz,2H),3.82(s,3H),3.27(s,3H).
应用例:有机电致发光器件的制作
将50mm*50mm*1.0mm的具有ITO(100nm)透明电极的玻璃基板在乙醇中超声清洗10分钟,再150度烘干后经过N2Plasma处理30分钟。将洗涤后的玻璃基板安装在真空蒸镀装置的基板支架上,首先再有透明电极线一侧的面上按照覆盖透明电极的方式蒸镀化合物HATCN,形成膜厚为5nm的薄膜,紧接着蒸镀一层HTM1形成膜厚为60nm的薄膜,再在HTM1薄膜上蒸镀一层HTM2形成膜厚为10nm的薄膜,然后,在HTM2膜层上再采用共蒸镀的模式蒸镀主体材料1、主体材料2和参杂化合物(对比化合物X、CPD X),膜厚为30nm,主体材料和参杂材料比例为45%:45%:10%。在发光层上再依次蒸镀ETL膜层(25nm)LiQ膜层(1nm),最后蒸镀一层金属Al(100nm)作为电极。
评价:
将上述器件进行器件性能测试,在各实施例和比较例中,使用恒定电流电源(Keithley2400),使用固定的电流密度流过发光元件,使用分光辐射俩都系(CS 2000)测试发光波谱。同时测定电压值以及测试亮度为初始亮度的90%的时间(LT90)。结果如下:
掺杂材料 | 启动电压V | 电流效率Cd/A | 峰值波长nm | LT90@3000nits | |
实施例1 | A1 | 4.77 | 41 | 523 | 140 |
实施例2 | A 3 | 4.73 | 44 | 525 | 143 |
实施例3 | A 28 | 4.71 | 46 | 528 | 149 |
实施例4 | A 39 | 4.68 | 51 | 527 | 177 |
实施例5 | A 71 | 4.69 | 48 | 525 | 172 |
实施例6 | A 82 | 4.68 | 53 | 523 | 189 |
实施例7 | A 89 | 4.73 | 45 | 529 | 158 |
实施例8 | A 100 | 4.78 | 51 | 531 | 186 |
实施例9 | A 111 | 4.81 | 49 | 529 | 176 |
实施例10 | A 125 | 4.67 | 51 | 533 | 169 |
实施例11 | A 168 | 4.73 | 47 | 535 | 181 |
实施例12 | A 197 | 4.69 | 54 | 534 | 191 |
对比例1 | 对比1 | 4.84 | 31 | 510 | 115 |
对比例2 | 对比2 | 4.86 | 38 | 517 | 136 |
由上面表格中的数据对比可知,使用本发明的化合物作为绿光掺杂剂的有机电致发光器件,相较于对比化合物在驱动电压、发光效率、器件寿命都表现出更加优越的性能。
上述结果表明本发明的化合物具有光、电化学稳定性高,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为绿色磷光材料,具有应用于OLED产业的可能。
Claims (12)
- 一种金属络合物,其具有式(1)所示的结构;其中R1-R18至少之一为式(2)所示的结构;其中:*表示与式(1)连接的位置;M独立的为Pt、Pd;X独立的表示O,S,Se,CRaRb;L1-L3各自独立的选自直接键合单键,O,S,Se,NRc,CRdRe,SO,SO2,PO(Rf)(Rg);L4为单键,O,取代的或未取代的C1-C20亚烷基、取代的或未取代的C3-C30亚环烷基、取代的或未取代的C1-C20亚杂烷基、取代的或未取代的C7-C30亚芳烷基,取代或未取代的C2-C20的亚烯基、取代的或未取代的C3-C30亚烷基硅基、取代的或未取代的C6-C30亚芳基、取代的或未取代的C3-C30亚杂芳基、取代的或未取代的C3-C30亚芳基硅基、取代或未取代的C0-C20的亚胺基;其余R1-R18、R101-R102和Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C20烷基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C20杂烷基、取代的或未取代的C7-C30芳烷基、取代的或未取代的C1-C20烷氧基、取代的或未取代的C6-C30芳氧基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C30烷基硅基、取代的或未取代的C6-C30芳基、取代的或未取代的C3-C30杂芳基、取代的或未取代的C3-C30芳基硅基、取代或未取代的C0-C20的胺基、氰基、腈、异腈、膦基;或者任意两个相邻的基团之间相互连接以形成环状结构或者并环结构;所述取代为被氘、卤素、C1-C4烷基、氰基所取代;R101、R102的取代个数独立的表示无取代到最大取代个数。
- 根据权利要求1-3任一所述的金属络合物,其中L4为单键、O及以下结构之一:其中:*表示与式(1)及式(2)连接的位置;Rx的个数表示无取代到最大取代个数,当Rx为多取代时,相邻的两个取代基可以互相连接以形成环状或并环结构;Rx和Ry独立地为氢、氘、卤素、取代的或未取代的C1-C20烷基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C20杂烷基、取代的或未取代的C7-C30芳烷基、取代的或未取代的C1-C20烷氧基、取代的或未取代的C6-C30芳氧基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C30烷基硅基、取代的或未取代的C6-C30芳基、取代的或未取代的C3-C30杂芳基、取代的或未取代的C3-C30芳基硅基、取代或未取代的C0-C20的胺基、氰基、腈、异腈、膦基。
- 根据权利要求4所述的金属络合物,其中R1、R2、R7、R8、R10、R11、R18、R101、R102、Ra、Rb、Rx和Ry独立地选自氢、氘、卤素、取代的或未取代的C1-C8烷基、取代的或未取代的C3-C10环烷基、取代的或未取代的C1-C8杂烷基、取代的或未取代的C7-C10芳烷基、取代或未取代的C2-C20的烯基、取代的或未取代的C3-C8烷基硅基、取代的或未取代的C6-C10芳基、取代的或未取代的C3-C10杂芳基、取代的或未取代的C3-C10芳基硅基、取代或未取代的C0-C6的胺基、氰基。
- 根据权利要求5所述的金属络合物,其中R1、R2、R7、R8、R10、R11、R18、R101、R102、Ra、Rb、Rx和Ry独立地选自氢、氘、卤素、取代的或未取代的C1-C8烷基、取代的或未取代的C3-C10环烷基、取代的或未取代的C1-C8杂烷基、取代的或未取代的苯基烷基、取代的或未取代的C6-C10芳基、取代的或未取代的C3-C10杂芳基。
- 根据权利要求6所述的金属络合物,其中R18为氘、取代或未取代的直链碳原子C1-C4 烷基、取代或未取代的C1-C6个环烷基,所述取代为被氘或卤素所取代。
- 根据权利要求6所述的金属络合物,其中R1和R2至少之一不为氢。
- 一种电致发光器件,其包括:阴极,阳极以及设置在阴极阳极之间的有机层,所述有机层至少一层包含权利要求1-9任一所述的金属络合物。
- 如权利要求11所述的电致发光器件,其中所述有机层包含发光层,所述金属络合物作为发光层中的绿色发光材料;或者其中所述有机层包含空穴注入层,所述金属络合物作为空穴注入层中的空穴注入材料。
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