CN113402561B - 一种基于螺芴结构的高色纯度铂(ii)配合物发光材料及其应用 - Google Patents
一种基于螺芴结构的高色纯度铂(ii)配合物发光材料及其应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 47
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000003446 ligand Substances 0.000 abstract description 14
- 238000001228 spectrum Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- 239000010410 layer Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002904 solvent Substances 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000295 emission spectrum Methods 0.000 description 11
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- 239000007924 injection Substances 0.000 description 9
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- 229910002027 silica gel Inorganic materials 0.000 description 9
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- 125000001072 heteroaryl group Chemical group 0.000 description 4
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- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
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- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- OPPSYCGZHQVDPM-UHFFFAOYSA-N 2-bromo-4-tert-butyl-1-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1Br OPPSYCGZHQVDPM-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical group NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明属于有机光电材料技术领域,特别涉及一种基于螺芴结构的高色纯度铂(II)配合物发光材料及其应用,可用于OLED显示和照明领域。所述铂(II)配合物具有通式(I)所示的结构。本发明所提供的发光材料,可以通过调节配体的结构刚性以及调控配体上取代基的结构和位置来调控四齿环金属铂(II)配合物的光物理性质,从而实现窄光谱发射、高发光色纯度的目标,其在OLED显示等领域有着广阔的应用前景。
Description
技术领域
本发明属于有机光电材料技术领域,特别涉及一种基于螺芴结构的高色纯度铂(II)配合物发光材料及其应用。
背景技术
OLED即有机发光二极管或有机发光器件,它通过电致发光将电能转化为光能,在开发新一代平板显示器和节能型固体光源方面具有很大的潜力。OLED显示技术具有如下优势:自发光、可弯曲、响应速度快、透明显示、具有驱动电压低、发光效率和分辨率高、对比度高、视角广等特点。它已成为新一代的全彩显示和照明技术,在手机、电脑、电视、可弯曲和折叠屏幕等电子产品领域有着广泛而巨大的应用前景。
发光元件有机半导体是有机电致发光元件中最关键的材料元件,而显示设备采用色纯度高的发光材料,可以尽可能地还原真实的色彩,带来更出色的色彩表现。但是目前可利用的材料仍有着低效率的发射以及色纯度低(发光光谱较宽)的缺点,利用光学过滤器除去不必要的颜色,结果就会导致显示屏的亮度、发光效率大幅度降低。因此,急需开发光谱窄及色纯度较高的发光材料。
发明内容
针对现有技术中存在的发光光谱较宽的问题,本发明的目的在于提供一种的具有窄光谱发射及高色纯度的四齿环金属铂(II)配合物发光材料,所述的发光材料可用于OLED显示和照明领域。
为实现上述目的,本发明提供了一种基于螺芴结构的高色纯度铂(II)配合物发光材料,所述的铂(II)配合物发光材料具有通式(I)所示的结构:
其中:
Ra、Rb、Rc和Rd各自独立地为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;
R1、R2、R3、R4、R5、R6和R7各自独立地表示单基取代、双基取代、三基取代、四基取代或者无取代,且R1、R2、R3、R4、R5、R6和R7各自独立地为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且两个或者多个邻近的R1、R2、R3、R4、R5、R6和R7各自独立或者选择性连接形成稠环。
进一步地,所述基于螺芴结构的高色纯度铂(II)配合物发光材料具体为下述结构所表示的化合物,但不局限于此:
进一步地,所述铂(II)配合物具有基于联苯基链接的刚性结构,以及螺芴联苯基团及其衍生物等大取代基调节其分子间作用力。
进一步地,所述基于螺芴结构的高色纯度铂(II)配合物发光材料应用于光学装置中。
进一步地,所述光学装置包括全彩显示器、光伏器件、发光显示器件、有机发光二极管或磷光有机发光二极管。
与现有技术相比,本发明的有益效果在于:本发明通过改变配体的桥连原子以及调控配体上的取代基结构和位置来调节金属铂(II)配合物的光物理性质。使用碳原子桥连的联苯基配体使得分子刚性增强,从而减少由于配体分子的旋转和振动而导致的非辐射跃迁,可实现窄光谱发射,提高材料的发射量子效率,提高发射光的颜色纯度。同时,我们在配体上引入螺芴环及其衍生物,通过增大分子间位阻抑制了准分子的形成,减少了分子间相互作用引起的三重态-三重态猝灭,利于量子效率的提高,提高分子的发光色纯度。本发明的磷光发光材料是一类光谱窄、色纯度高的磷光发光材料,在OLED材料领域有着很大的应用前景。
附图说明
图1为具体实施方式中的铂(II)配合物Pt-1在室温下、二氯甲烷溶液中的发射光谱图;
图2为具体实施方式中的铂(II)配合物Pt-1-t在室温下、二氯甲烷溶液中的发射光谱图;
图3是具体实施方式中的铂(II)配合物Pt-1和Pt-1-t在室温下、二氯甲烷溶液中的发射光谱图组合图。
图4为有机发光元件的结构示意图。
具体实施方式
可通过参考以下具体实施方式和其中包含的实施例而更容易地理解本公开。
以下实施例向本领域普通技术人员提供如何制造和评价本发明描述的化合物及其OLED器件,所述实施例仅是本公开内容的示范且不圈定限制范围。尽管已经尽力确保关于数值(例如,量、温度等)的准确性,但是应当考虑一些误差和偏差。除非另外说明,否则温度是以℃为单位或者在环境温度下,且压力是在大气压下或附近。
下面例子中提供了新化合物的制备方法,但是该类化合物的制备不受限于此方法。在该专业技术领域中,由于本专利中的所保护的化合物易于修饰制备,因此,其制备可以采用下列所列举的方法或者采用其他的方法。下面的例子仅作为实施例,并不用于限制该专利的保护范围。温度、催化剂、浓度、反应物以及反应过程均可以改变,用于对不同的反应物,选择不同条件制备所述化合物。
在Varian Liquid State NMR仪器上进行1H NMR(500MHz)和13C NMR(126MHz)图谱测试。如无特别说明,核磁均用DMSO-d6或者含0.1%TMS的CDCl3做溶剂,其中1H NMR谱若以CDCl3作溶剂时,溶剂中如有内标四甲基硅烷,化学位移则参照四甲基硅烷(δ=0.00ppm);否则,若以CDCl3为溶剂,1H NMR图谱化学位移则参照残留溶剂(δ=7.26ppm);以DMSO-d6作溶剂时,以TMS(δ=0.00ppm)或残留DMSO峰(δ=2.50ppm)或残留水峰(δ=3.33ppm)做内标。13CNMR谱中,以CDCl3(δ=77.00ppm)或者DMSO-d6(δ=39.52ppm)作为内标。1H NMR谱图数据中:s=singlet,单重峰;d=doublet,二重峰;t=triplet,三重峰;q=quartet,四重峰;p=quintet,五重峰;m=multiplet,多重峰;br=broad,宽峰。
合成路线
通用合成步骤如下:
实施例1:发光材料Pt 1可按如下路线合成:
(1)中间体1-OH的合成:向带有磁力搅拌子的干燥三口烧瓶中加入邻溴联苯(2.56g,11.0mmol,1.7当量),在氮气保护下加入四氢呋喃(70mL)。反应装置置于乙醇浴中,用液氮降温至-78℃,然后再缓缓滴加正丁基锂(7.00mL,11.00mmol,1.7当量,1.60mol/L正己烷溶液),反应3小时后再加入3-溴苯基-2-吡啶甲酮(1.80mg,6.90mmol,1.00当量),室温搅拌24小时。反应液用氯化铵的饱和溶液淬灭,再加入乙酸乙酯萃取三次,水层用乙酸乙酯萃取两次。合并有机相,用无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯=20:1-10:1,得到产物A-OH,油状无色透明液体2.60g,收率90%。1H NMR(500MHz,DMSO):δ6.71(s,1H),6.88-6.86(m,3H),6.95(t,J=7.0Hz,2H),7.03-6.98(m,2H),7.06(ddd,J=1.0,5.0,6.0Hz,1H),7.14(t,J=8.0Hz,1H),7.25(td,J=1.5,7.5Hz,1H),7.33-7.29(m,3H),7.44-7.42(m,1H),7.47(td,J=1.5,7.5Hz,1H),7.59(t,J=2.0Hz,1H),8.35(dq,J=0.5,4.5Hz,1H)。
(2)中间体1-Br的合成:向带有磁力搅拌子的干燥三口烧瓶中加入A-OH(1.00g,2.40mmol,1.00当量)、醋酸(25mL),然后加入浓硫酸(1mL)、醋酸酐(1mL)。将三口烧瓶放入带有磁力搅拌的油浴锅中,在130℃下搅拌反应12小时,薄层色谱监测至原料反应完毕。反应冷却至室温后在减压蒸馏中除去溶剂,再用碳酸钠饱和溶液调节PH至弱碱性。然后加入乙酸乙酯萃取三次,水层用乙酸乙酯萃取两次,合并有机相用无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯=10:1-5:1,得到白色固体920mg,收率96%。1H NMR(500MHz,DMSO-d6):δ7.04-6.98(m,3H),7.20(t,J=7.5Hz,1H),7.28(ddd,J=6.0,5.0,1.0Hz,1H),7.35(td,J=7.5,1.0Hz,2H),7.40(ddd,J=3.0,2.0,1.0Hz,1H),7.44(td,J=7.5,1.0Hz,2H),7.57(d,J=7.5Hz,2H),7.66(td,J=7.5,2.0Hz,1H),7.95(d,J=7.5Hz,2H),8.59(ddd,J=2.5,1.5,0.5Hz,1H)。
(3)中间体2-Br的合成:向带有磁力搅拌子的干燥三口烧瓶中加入3-溴咔唑(500mg,2.03mmol,1.00当量),碘化亚铜(39mg,0.20mmol,10mol%),1-甲基咪唑(33mg,0.41mmol,20mol%)和叔丁醇锂(325mg,4.06mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入2-溴吡啶(353mg,2.23mmol,1.1当量)和甲苯(10mL)。该混合物在120℃的油浴锅中搅拌反应24小时,薄层色谱监测至原料反应完毕。冷却至室温,将反应液减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=100:1-50:1,得到产物2-Br,无色油状液体640mg,收率97%。1H NMR(500MHz,CDCl3):δ7.36-7.32(m,2H),7.43(dd,J=8.0,1.5Hz,1H),7.48-7.45(m,1H),7.63(d,J=8.0Hz,1H),7.78(d,J=8.0Hz,1H),7.98-7.96(m,2H),8.01(d,J=1.5Hz,1H),8.09(d,J=8.0Hz,1H),8.75-8.75(m,1H)。
(4)中间体2-B的合成:向带有磁力搅拌子的干燥封管中加入2-Br(1.00g,3.09mmol,1.00当量),双联频那醇硼酸酯(1.18g,4.64mmol,1.50当量),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(68mg,0.09mmol,3mol%),迅速加入醋酸钾,然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。再将该封管放入带有磁力搅拌的油浴锅中,在80℃的油浴锅中搅拌反应1天,薄层色谱监测至原料反应完毕。将反应冷却至室温,加入乙酸乙酯稀释,有机相用水洗涤两次,水层用乙酸乙酯萃取两次。合并有机相,无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂,所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯=20:1-10:1,得到白色固体785mg,收率69%。1H NMR(500MHz,CDCl3):δ1.37(s,12H),7.34-7.30(m,2H),7.48-7.44(m,1H),7.67(d,J=9.0Hz,1H),7.78(d,J=7.5Hz,1H),7.83(d,J=8.5Hz,1H),7.97(td,J=8.0,1.5Hz,1H),8.15-8.12(m,2H),8.20(s,1H),8.76(d,J=3.5Hz,1H)。
(5)配体Ligand 1的合成:向带有磁力搅拌子的干燥三口烧瓶中加入2-B(350mg,0.95mmol,1.00当量)、1-Br(377mg,0.95mmol,1.00当量)、四三苯基膦钯(55mg,0.047mmol,5mol%)和碳酸钾(261mg,1.89mmol,2.0当量)。然后抽换氮气三次,在氮气保护下加入1,4-二氧六环(12mL)和水(3mL)。再将该三口烧瓶放入带有磁力搅拌的油浴锅中,在90℃下搅拌反应24小时,薄层色谱监测至原料反应完毕。将反应冷却至室温,减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯/二氯甲烷=20:1:1-10:1:1,得到L(bp-1),白色固体528mg,收率98%。1H NMR(500MHz,DMSO-d6):δ6.98-6.97(m,1H),7.14(d,J=8.0Hz,1H),7.23(t,J=1.5Hz,1H),7.29(ddd,J=5.5,5.0,0.5Hz,1H),7.35-7.31(m,4H),7.48-7.42(m,4H),7.56-7.54(m,2H),7.63(d,J=8.0Hz,2H),7.67(td,J=8.0,2.0Hz,1H),7.79-7.77(m,3H),7.95(d,J=7.5Hz,2H),8.14(td,J=8.0,2.0Hz,1H),8.26-8.22(m,2H),8.59(dd,J=4.5,1.0Hz,1H),8.72(dd,J=5.0,1.5Hz,1H)。
(6)Pt 1的合成:向带有磁力搅拌子的干燥三口烧瓶中加入Ligand 1(200mg,0.36mmol,1.00当量)和二氯化铂(100mg,0.37mmol,1.05当量),然后抽换氮气三次,在氮气保护下加入苯甲睛(17mL)。将三口烧瓶放入带有磁力搅拌的油浴锅中,在180℃下搅拌反应1天,薄层色谱监测至原料反应完毕。待反应冷却至室温后,在减压蒸馏中除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/二氯甲烷=1:1-1:2,得到橙红色固体213mg,收率79%。1H NMR(500MHz,DMSO-d6):δ6.05-6.03(m,1H),6.53(t,J=7.0Hz,1H),7.10(d,J=8.0Hz,2H),7.17-7.16(m,1H),7.27(s,1H),7.39-7.32(m,3H),7.50-7.47(m,1H),7.56-7.53(m,2H),7.62(d,J=7.5Hz,2H),7.66-7.65(m,1H),7.91-7.87(m,2H),8.13-8.06(m,3H),8.27-8.23(m,1H),8.35(d,J=8.5Hz,1H),8.73(dd,J=6.0,1.5Hz,1H),9.11(dd,J=6.0,1.5Hz,1H),9.51(s,1H)。
实施例2:发光材料Pt 1-t可按如下路线合成:
(1)中间体1-OH-t的合成:向带有磁力搅拌子的干燥三口烧瓶中加入2-溴-4,4'-二叔丁基联苯(1.26g,3.63mmol,1.0当量),在氮气保护下加入四氢呋喃(40mL)。反应装置置于乙醇浴中,用液氮降温至-78℃,然后再缓缓滴加正丁基锂(2.30mL,3.63mmol,1.0当量,1.60mol/L正己烷溶液),反应3小时后再加入3-溴苯基-2-吡啶甲酮(1.00mg,3.80mmol,1.05当量),室温搅拌24小时。反应液用氯化铵的饱和溶液淬灭,再加入乙酸乙酯萃取三次,水层用乙酸乙酯萃取两次。合并有机相,用无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯=40:1-20:1,得到产物1-OH-t,油状无色透明液体1.50g,收率78%。1H NMR(500MHz,CDCl3):δ1.21(s,9H),1.25(s,9H),6.89(d,J=8.0Hz,2H),7.06-7.00(m,4H),7.13-7.07(m,4H),7.28(t,J=6.5Hz,2H),7.34(dd,J=8.0,1.5Hz,1H),7.50(t,J=7.5Hz,1H),7.54(s,1H),8.37(d,J=4.5Hz,1H)。
(2)中间体1-Br-t的合成:向带有磁力搅拌子的干燥三口烧瓶中加入1-Br-t(1.50g,2.84mmol,1.00当量)、醋酸(25mL),然后加入浓硫酸(1.2mL)、醋酸酐(1mL)。将三口烧瓶放入带有磁力搅拌的油浴锅中,在130℃下搅拌反应12小时,薄层色谱监测至原料反应完毕。反应冷却至室温后在减压蒸馏中除去溶剂,再用碳酸钠饱和溶液调节PH至弱碱性。然后加入乙酸乙酯萃取三次,水层用乙酸乙酯萃取两次,合并有机相用无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯=20:1-10:1,得到油状无色透明液体1.5g,收率99%。1H NMR(500MHz,CDCl3):δ1.30(s,18H),6.99(d,J=6.0Hz,1H),7.16(s,1H),7.25-7.21(m,2H),7.40(dd,J=8.0,1.5Hz,2H),7.51(s,1H),7.60(s,1H),7.65(d,J=8.0Hz,3H),7.68-7.66(m,2H),8.71(s,1H)。
(3)配体Ligand 1-t的合成:向带有磁力搅拌子的干燥三口烧瓶中加入2-B(381mg,1.03mmol,1.05当量)、1-Br-t(500mg,0.98mmol,1.00当量)、四三苯基膦钯(57mg,0.049mmol,5mol%)和碳酸钾(271mg,1.96mmol,2.0当量)。然后抽换氮气三次,在氮气保护下加入1,4-二氧六环(12mL)和水(3mL)。再将该三口烧瓶放入带有磁力搅拌的油浴锅中,在90℃下搅拌反应48小时,薄层色谱监测至原料反应完毕。将反应冷却至室温,减压蒸馏除去溶剂后加入乙酸乙酯稀释,有机相用水洗涤两次,水层用乙酸乙酯萃取两次。合并有机相,无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/乙酸乙酯/二氯甲烷=20:3:1-15:3:1,得到Ligand 1-t,白色固体520mg,收率79%。1H NMR(400MHz,DMSO-d6):δ1.22(s,18H),7.08-7.03(m,2H),7.19(s,1H),7.26(t,J=6.0Hz,1H),7.40-7.31(m,3H),7.47-7.42(m,3H),7.55-7.52(m,2H),7.68-7.64(m,3H),7.80-7.76(m,5H),8.11(t,J=7.6Hz,1H),8.24(t,J=6.4Hz,2H),8.61(d,J=4.0Hz,1H),8.70(d,J=4.8Hz,1H)。
(4)Pt 1-t的合成:向带有磁力搅拌子的干燥三口烧瓶中加入Ligand 1-t(300mg,0.45mmol,1.00当量)和二氯化铂(126mg,0.47mmol,1.05当量),然后抽换氮气三次,在氮气保护下加入苯甲睛(20mL)。将三口烧瓶放入带有磁力搅拌的油浴锅中,在180℃下搅拌反应3天,薄层色谱监测至原料反应完毕。反应冷却至室温后在减压蒸馏中除去溶剂。所得粗产品用硅胶层析柱分离,洗脱剂:石油醚/二氯甲烷=3:1-1:1,得到橙黄色固体220mg,收率56%。1H NMR(500MHz,DMSO-d6):δ0.98(s,9H),1.38(s,9H),6.09(dd,J=8.0,1.0Hz,1H),6.54(t,J=7.5Hz,1H),7.08(d,J=7.5Hz,1H),7.16(dd,J=7.5,0.5Hz,1H),7.34-7.28(m,3H),7.39-7.36(m,1H),7.50-7.47(m,1H),7.56-7.53(m,2H),7.62(d,J=7.5Hz,1H),7.70-7.65(m,2H),7.91-7.87(m,1H),7.95(d,J=7.0Hz,1H),8.06(d,J=8.5Hz,1H),8.12(dd,J=7.5,0.5Hz,1H),8.26-8.22(m,1H),8.32(d,J=8.5Hz,1H),8.74-78.73(m,1H),9.12(dd,J=5.5,1.5Hz,1H),9.75(s,1H)。
以上所述的仅是本发明的实施方式,在此应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出改进,但这些均属于本发明的保护范围。
性能评价
以下对本发明的上述实施例中所制备的配合物进行光物理分析。
光物理分析:发射光谱均在HITACHI F-7000光谱仪上测试完成,实施例1和2合成的发光材料的发射光谱图如图1~2。所述配合物发光材料发射光谱的测试条件:在室温下测试,所有样品均为二氯甲烷(色谱级)稀溶液(10-5-10-6M),且光谱的半峰宽为谱峰高一半处的峰宽度,即通过峰高的中点作平行于峰底的直线,此直线与峰两侧相交两点之间的距离。
表1.室温下磷光发光材料在二氯甲烷溶液中的光物理性质
发光材料 | Peak/nm | FWHM/nm |
Pt 1 | 560.2 | 27.8 |
Pt 1-t | 560.6 | 27.6 |
注:Peak是指发光材料在室温下、二氯甲烷溶液中发射光谱的发射峰值。FWHM是指发射光谱的半峰宽。
图1~图2是表1中两种发光材料在室温下、二氯甲烷溶液中的发射光谱。由以上数据可知,此类联苯基-咔唑基和螺芴环的四齿环金属铂(II)配合物在室温下、二氯甲烷溶液中的最大发射峰均在560-561nm,且半峰宽非常小,为27-28nm,均为窄光谱发射的绿光发光材料,量子效率可达50%以上。图3是实施例1、2合成的两种发光材料在室温下、二氯甲烷溶液中的发射光谱图组合图。
此外,本发明的实施方式还提供一种光学装置,其包含所述的基于螺芴结构的高色纯度铂(II)配合物发光材料中的一种或多种。
可选地,所述器件包括全彩显示器、光伏器件、发光显示器件、机发光二极管、磷光有机发光二极管。
在有机发光元件中,从正负两电极向发光材料中注入载子,产生激发态的发光材料并使其发光。通过通式(1)代表的本发明的络合物可作为磷光发光材料应用于有机光致发光元件或有机电致发光元件等优异的有机发光元件。有机光致发光元件具有在衬底上至少形成了发光层的结构。另外,有机电致发光元件具有至少形成了阳极、阴极、及阳极和阴极之间的有机层的结构。有机层至少包含发光层,可以仅由发光层构成,也可以除发光层以外具有1层以上的有机层。作为这种其它有机层,可以列举空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子注入层、电子传输层、激子阻挡层等。空穴传输层也可以是具有空穴注入功能的空穴注入传输层,电子传输层也可以是具有电子注入功能的电子注入传输层。具体的有机发光元件的结构示意如图4所示。在图4中,从下到上共7层,依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极,其中发光层为客体材料掺杂入主体材料的混合层。
本发明的磷光发光材料作为客体材料掺杂入主体材料制成发光层可应用于OLED器件,结构表示为:
ITO/HATCN(10nm)/TAPC(65nm)/主体材料:Pd(ACzCz-2)(10wt.%,20nm)/TmPyPB(55nm)/LiF/Al
其中,ITO为透明阳极;HATCN是空穴注入层,TAPC是空穴传输层,主体材料分别为mCBP和26mCPy,TmPyPB为电子传输层,LiF为电子注入层,Al为阴极。括号中单位为纳米(nm)的数字为薄膜的厚度。
器件中应用材料的分子式如下:
需要说明的是,所述结构为本发明磷光材料的一个应用的举例,不构成本发明所示磷光材料的具体OLED器件结构的限定,磷光发光材料也不限于实施例中所表示的化合物。
本领域的普通技术人员可以理解,上述各实施方式是实现本发明的具体实施例,而在实际应用中,可以在形式上和细节上对其作各种改变,而不偏离本发明的精神和范围。例如,在不背离本发明的精神的情况下,这里描述的许多取代基结构可以用其它结构代替。
Claims (3)
1.一种基于螺芴结构的高色纯度铂(II)配合物发光材料,其特征在于,所述铂(II)配合物具有如下之一的结构:
。
2.一种权利要求1中任一项所述的基于螺芴结构的高色纯度铂(II)配合物发光材料在光学装置的应用。
3.根据权利要求2所述的应用,其特征在于,所述光学装置为全彩显示器、光伏器件、发光显示器件或有机发光二极管。
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