CN108948094B - 一类镶接“蝴蝶”结构的c^n双齿有机共轭配体及其环金属铱配合物单分子白光材料 - Google Patents
一类镶接“蝴蝶”结构的c^n双齿有机共轭配体及其环金属铱配合物单分子白光材料 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 22
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000004793 Polystyrene Substances 0.000 claims abstract description 6
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 abstract 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 abstract 1
- -1 dicyclic metal complex Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229950000688 phenothiazine Drugs 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 238000000103 photoluminescence spectrum Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
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- 239000001257 hydrogen Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
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- 230000007704 transition Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LCCZTROJRJFXNV-UHFFFAOYSA-N (2,6-difluoropyridin-3-yl)boronic acid Chemical compound OB(O)C1=CC=C(F)N=C1F LCCZTROJRJFXNV-UHFFFAOYSA-N 0.000 description 1
- LQWXEEDCMLEVHU-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)pyridine Chemical compound N1=CC=CC=C1C1=NNN=N1 LQWXEEDCMLEVHU-UHFFFAOYSA-N 0.000 description 1
- AIEATTRZKVGMBO-UHFFFAOYSA-N 2-bromo-4-fluoropyridine Chemical compound FC1=CC=NC(Br)=C1 AIEATTRZKVGMBO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 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
- C07F15/0033—Iridium 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
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- 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
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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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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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明涉及一类镶接“蝴蝶”结构的C^N双齿有机共轭配体及环金属铱配合物单分子白光材料。该类白光材料具有以下特点:i)C^N双齿有机共轭配体是镶接吩噁嗪、吩噻嗪等“蝴蝶”结构的C^N双齿有机共轭配体,通过外部环境的微扰,可以诱导“蝴蝶”结构的旋转,实现C^N双齿配体发光颜色从蓝光至红光的调控;ii)环金属铱配合物是以C^N双齿有机共轭配体为配体,形成的双环金属配合物。该配合物具有深蓝光或蓝光磷光发色团内核结构和镶接的“蝴蝶”结构,利用配合物的不同激发态的复合发光产生白光。该类白光材料在溶液和掺杂聚苯乙烯薄膜中均得到了单分子白光发射。通过简单的镶接“蝴蝶”结构,本发明实现了单核环金属铱配合物的单分子光致白光发射。
Description
技术领域
本发明涉及发光与显示技术领域,具体涉及一类镶接“蝴蝶”结构的C^N双齿有机共轭配体及其环金属铱配合物单分子有机白光材料。
背景技术
有机电致发光二极管(OLEDs)被誉为新一代照明和显示技术,因具有主动发光、发光效率高、驱动电压低、能耗低、重量轻等优点,在固态照明和平板显示应用中显示了巨大的发展前景,一直是新材料、节能环保领域的发展重点和研究热点[1]。目前,OLEDs技术已经广泛应用在手机、照相机和仪表等小尺寸显示屏领域,大尺寸的OLEDs电视也在接近实用化。其中,文献报道的大多数白光发光二极管大都是依赖于几种不同的三基色发光材料(红/绿/蓝或蓝/橙色)的复合发光而成,从400nm到700nm跨度整个可见光谱;但多种发光材料的复合结构会导致器件制备复杂、工艺成本高、使用寿命短和发光色度不稳定等问题[2-5]。因此,开发高效稳定的单分子有机白光材料对于发展高效低成本OLEDs具有重要的现实意义。
目前,基于单分子白光发射材料主要是由小分子,低聚物和聚合物等荧光材料,以及具有平面结构的环金属铂配合物磷光材料构成。但荧光材料的理论内量子效率仅为25%,荧光型单分子白光材料的应用受到较大的限制;环金属铂配合物容易聚集,产生发光淬灭现象,制约了发光效率的提升。虽然环金属铱配合物宽带发光材料也有报道,但高效发光的环金属铱配合物单分子白光材料种类非常少,且在器件中的发光效率非常低。2009年,Nazeeruddin小组[6]报道了一种环金属铱配合物(N966),呈现了白色的光致发光和电致发光,波长范围从440nm到800nm,半峰宽为165nm。这是迄今为止报道为数不多的环金属铱配合物单分子白光材料。
因此,发展发光效率高、色纯度稳定、器件性能稳定的环金属铱配合物单分子有机白光材料具有重要的意义。
附:主要参考文献
[1]S.Reineke,F.Lindner,G.Schwartz,N.Seidler,K.Walzer,B.Lussem,K.Leo,Nature,2009, 459,234.
[2]C.Duan,C.Han,R.Du,Y.Wei,H.Xu,Adv.Opt.Mater.2018,1800437.
[3]C.Zhou,S.Zhang,Y.Gao,H.Liu,T.Shan,X.Liang,B.Yang,Y.Ma,Adv.Funct.Mater. 2018,1802407.
[4]G.Sarada,W.Cho,A.Maheshwaran,V.G.Sree,H.-Y.Park,Y.-S.Gal,M.Song,S.-H.Jin, Adv.Funct.Mater.2017,27,1701002.
[5]K.T.Kamtekar,A.P.Monkman,M.R.Bryce,Adv.Mater.2010,22,572.
[6]H.J.Bolink,F.De Angelis,E.Baranoff,C.Klein,S.Fantacci,E.Coronado,M.Sessolo,K. Kalyanasundaram,M.Gratzel,M.K.Nazeeruddin,Chem.Commun.2009,4672-4674.
发明内容
本发明旨在提供一类镶接“蝴蝶”结构的C^N双齿有机共轭配体及其环金属铱配合物单分子白光材料。
本发明提供的一类镶接“蝴蝶”结构的C^N双齿有机共轭配体及其环金属铱配合物单分子白光材料分别具有以下通式(1)和(2)结构:
所述式中,Ar选自如下基团:
其中Y为以下杂原子:O、S、Se等;
其中R为以下吸电子基团:氟原子、氰基、碳原子数为C1~C20的酯基;
所述式中,R1,R2,R3和R4独立选自如下吸电子基团:-F、-CF3
所述式中,X独立选自如下原子:-C-,-N-
所述式中,L选自N^O或N^N型阴离子配体,如下基团:
其中Ar选自如下具有“蝴蝶”结构的基团:
其中Y为杂原子基团,如:O、S、Se等;
其中R为吸电子基团,如:氟原子、氰基、碳原子数为C1~C20的酯基
附图说明
【图1】为本发明实施例1制得的C^N双齿有机共轭配体dfpypy-4-PTZ在DCM、THF和Tol中的紫外可见吸收光谱图
【图2】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic在DCM、THF、Tol和薄膜中的紫外可见吸收光谱图
【图3】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic在DCM、THF和Tol中的紫外可见吸收光谱图
【图4】为本发明实施例1制得的C^N双齿有机共轭配体dfpypy-4-PTZ在DCM、THF、Tol和薄膜的光致发光光谱图
【图5】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic在DCM、THF、Tol和薄膜中的光致发光光谱图和CIE色坐标图
【图6】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2Ir(pytz)在DCM、THF、Tol和薄膜中的光致发光光谱图和CIE色坐标图
【图7】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2Ir(pytz)在聚苯乙烯(PS)中掺杂不同质量分数的光致发光光谱图和CIE色坐标图
【图8】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic的单晶结构图
【图9】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2Ir(pytz)的单晶结构图
【图10】为本发明实施例1制得的化合物2-Br-4-PTZPy的核磁氢谱图
【图11】为本发明实施例1制得的C^N双齿有机共轭配体dfpypy-4-PTZ的核磁氢谱图
【图12】为本发明实施例1制得的C^N双齿有机共轭配体dfpypy-4-PTZ的核磁碳谱图
【图13】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic的核磁氢谱图
【图14】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2IrPic的核磁碳谱图
【图15】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2Ir(pytz)的核磁氢谱图
【图16】为本发明实施例1制得的配合物(dfpypy-4-PTZ)2Ir(pytz)的核磁碳谱图
具体实施方案
为了更清楚的说明本发明,下面结合优选实施例和附图对本发明作进一步说明。本领域技术人员应当理解,下面所描述的具体内容是说明性的而非限制性的,不因以此限制本发明的保护范围。
下面结合附图对本发明的具体实施方式作进一步详细说明。
本发明中,制备方法如无特殊说明均为常规方法。所用的原料如无特别说明均可以从公开的商业途径获得,所述百分比如无特殊说明均为质量百分比。本发明提供的一系列新型环金属铱配合物,所有的反应条件都是在众所周知的适合条件下进行。
实施例1
一类镶接“蝴蝶”结构的C^N双齿有机共轭配体及其环金属铱配合物单分子白光材料 (dfpypy-4-PTZ)2IrPic和(dfpypy-4-PTZ)2Ir(pytz)的制备。
其合成路线如下:
化合物1(2-Br-4-PTZPy)的制备
在250mL单口瓶中,依次加入吩噻嗪(PTZ)(5.0g,25.13mmol)、2-溴-4-氟吡啶(4.20 g,23.87mmol)、氢化钠(60%)(5.02g,125.65mmol)和150mL新蒸甲苯,磁力搅拌、氮气保护,回流反应24h。冷却至室温,过滤,用二氯甲烷清洗滤渣,收集滤液,减压蒸馏除去溶剂,剩余物以石油醚(PE)和二氯甲烷(DCM)混合溶剂为洗脱剂(PE:DCM=1:1,V:V),柱色谱分离得淡黄色固体粉末4.57g(产率:51.4%)。1H NMR(500MHz,CDCl3)δ7.95(d,J=6.0 Hz,1H),7.56–7.49(m,4H),7.42(td,J=7.7,1.4Hz,2H),7.30(td,J=7.6,1.3Hz,2H),6.96(d,J =2.3Hz,1H),6.76(dd,J=6.0,2.4Hz,1H).核磁氢谱图如图10所示。
化合物2(dfpypy-4-PTZ)的制备
在200mL单口瓶中,依次加入化合物1(3.75g,12.08mmol)、2,6-二氟吡啶-3-硼酸(2.1 g,13.29mmol)、Pd(PPh3)4(698mg,0.604mmol)、30.2mL K2CO3溶液(2M,60.4mmol)和60mL四氢呋喃(THF)溶液,氮气保护,加热至80℃,搅拌反应12h。冷却至室温,倒入250 mL的分液漏斗中,用乙酸乙酯(3×50mL)萃取。有机相经水洗,用无水硫酸镁干燥,过滤,减压蒸馏除去溶剂,剩余物以石油醚(PE)和乙酸乙酯(EA)混合溶剂为洗脱剂(PE:EA= 4:1,V:V),柱色谱分离得淡黄色固体粉末3.71g(产率:78.7%)。1H NMR(400MHz,CDCl3)δ 8.55(dd,J=17.5,8.0Hz,1H),8.32(d,J=5.9Hz,1H),7.57(dd,J=7.9,1.0Hz,2H),7.52(dd,J =7.8,1.2Hz,2H),7.43(d,J=1.5Hz,2H),7.32–7.20(m,2H),6.90(dd,J=8.2,2.9Hz,1H), 6.85(dd,J=5.9,2.5Hz,1H).13C NMR(126MHz,CDCl3)δ152.53,151.06,150.34,146.04,139.75,135.16,129.18,127.48,126.97,108.41,107.44,106.80,106.52.核磁氢谱图如图11所示,核磁碳谱图如图12所示。
化合物3的制备
在200mL单口瓶中,依次加入化合物2(1.25g,3.2mmol),三水合三氯化铱(477mg,1.6mmol),60mL乙二醇单乙醚和20mL蒸馏水,氮气保护,加热至130℃,搅拌反应18 h。冷却至室温,倒入盛有250mL蒸馏水的烧杯中,析出固体,抽滤,所得到的固体分别用蒸馏水、石油醚和正己烷洗涤,干燥得到黄绿色氯桥联固体1.02g,未经处理直接投下一步。
配合物(dfpypy-4-PTZ)2IrPic的制备
在100mL单口瓶中,依次加入化合物3(500mg,0.249mmol)、吡啶甲酸(Pic)(92mg,0.747mmol)、无水碳酸钠(Na2CO3)(132mg,1.25mmol)、60mL THF和20mL无水甲醇 (CH3OH),氮气保护,加热至90℃,搅拌反应12h。冷却至室温,倒入250mL的分液漏斗中,用DCM(3×50mL)萃取,有机相经水洗,用无水硫酸镁干燥,过滤,减压蒸馏除去溶剂,剩余物以DCM:EA混合溶剂(5:1,V:V)为洗脱剂,柱色谱分离得到淡黄色固体粉末,用DCM和CH3OH重结晶,得到产品317mg(产率:58.4%)。1H NMR(500MHz,CDCl3)δ 8.28(d,J=7.8Hz,1H),8.20(d,J=6.9Hz,1H),7.95–7.86(m,2H),7.82(s,1H),7.66(d,J=5.3 Hz,1H),7.62(dd,J=7.9,0.9Hz,2H),7.60–7.52(m,6H),7.50–7.41(m,4H),7.40–7.36(m, 1H),7.32(dd,J=18.9,7.6Hz,4H),6.90(d,J=6.9Hz,1H),6.79(dd,J=6.9,2.8Hz,1H),6.57 (dd,J=6.9,2.9Hz,1H),5.92(s,1H),5.74(s,1H).13C NMR(126MHz,CDCl3)δ172.39,171.19, 170.47,162.78,161.37,153.63,151.29,148.21,147.95,147.62,138.76,138.53,135.40,135.19,129.37,128.53,127.59,127.27,109.90,107.13,106.52.MALDI-TOF-MS(m/z):calcd forC50H28F4N7O2S2Ir,1091.13;found,1129.953[M+39]+.核磁氢谱图如图13所示,核磁碳谱图如图14所示。
配合物(dfpypy-4-PTZ)2Ir(pytz)的制备
在100mL单口瓶中,依次加入化合物3(500mg,0.249mmol)、5-(2-吡啶基)-1H-四唑(pytzH)(110mg,0.747mmol)、无水碳酸钠(Na2CO3)(132mg,1.25mmol)、60mL THF和20 mLCH3OH,氮气保护,加热至90℃,搅拌反应12h。冷却至室温,倒入250mL分液漏斗中,用DCM(3×50mL)萃取,有机相经水洗,用无水硫酸镁干燥,过滤,减压蒸馏除去溶剂,剩余物以DCM:EA混合溶剂(3:1,V:V)为洗脱剂,柱色谱分离得到淡黄色固体粉末,用DCM和CH3OH重结晶,得到产品352mg(产率:63.2%)。1H NMR(500MHz, CDCl3)δ8.41(d,J=7.9Hz,1H),7.95(td,J=7.8,1.5Hz,1H),7.85(dt,J=17.1,3.2Hz,2H), 7.72(d,J=5.3Hz,1H),7.61–7.49(m,8H),7.42(dtd,J=9.1,7.8,1.3Hz,4H),7.31(td,J=8.7, 1.3Hz,4H),7.06(d,J=7.0Hz,1H),6.89(d,J=7.0Hz,1H),6.57(dd,J=7.0,2.9Hz,1H),6.48 (dd,J=7.0,2.9Hz,1H),5.95(s,1H),5.87(s,1H).13C NMR(126MHz,CDCl3)δ163.31, 153.52,149.58,149.34,149.09,147.68,139.49,138.59,135.36,135.08,129.35,127.61,127.20, 126.13,123.21,107.61,107.31.MALDI-TOF-MS(m/z):calcd for C50H28F4N11S2Ir,1115.15; found,1116.225[M+1]+.核磁氢谱图如图15所示,核磁碳谱图如图16所示。
实施例2
实施例1中的C^N双齿有机共轭配体dfpypy-4-PTZ,配合物(dfpypy-4-PTZ)2IrPic和 (dfpypy-4-PTZ)2Ir(pytz)的紫外-可见吸收光谱测试。
将dfpypy-4-PTZ、(dfpypy-4-PTZ)2IrPic和(dfpypy-4-PTZ)2Ir(pytz)分别溶解在DCM、 THF和Tol中配成10-5M溶液,测试其溶液的紫外可见吸收光谱。图1为dfpypy-4-PTZ溶液的紫外可见吸收光谱,图2为(dfpypy-4-PTZ)2IrPic溶液及其薄膜的紫外可见吸收光谱,图3为(dfpypy-4-PTZ)2Ir(pytz)溶液及其薄膜的紫外可见吸收光谱。
由图1可知,配体dfpypy-4-PTZ呈现了2个吸收峰,分别位于短波长的243nm和长波长的277nm处;其中短波长吸收峰归属于分子π-π*的跃迁吸收;长波段吸收峰归属于分子内给体单元到受体单元的电荷转移(ICT)作用。由图2可知,配合物(dfpypy-4-PTZ)2IrPic的紫外-可见吸收出现了多个吸收峰,主要分为两大类:从230nm到304nm区间的短波长吸收峰归属于有机共轭配体中心的π-π*的跃迁吸收;从304nm到446nm区间的长波长吸收峰归属于MLCT、3MLCT以及ICT的混合态吸收跃迁。
由图3可知,配合物(dfpypy-4-PTZ)2Ir(pytz)的紫外-可见吸收也出现了多个吸收峰,主要分为两大类:从233nm到301nm区间的短波长吸收峰归属于有机共轭配体中心的π-π* 的跃迁吸收;从301nm到422nm区间的长波长吸收峰归属于MLCT、3MLCT以及ICT的混合态吸收跃迁。
实施例3
实施例1中的C^N双齿有机共轭配体dfpypy-4-PTZ,配合物(dfpypy-4-PTZ)2IrPic和 (dfpypy-4-PTZ)2Ir(pytz)的光致发光光谱测试。
将dfpypy-4-PTZ、(dfpypy-4-PTZ)2IrPic和(dfpypy-4-PTZ)2Ir(pytz)分别溶解在DCM、THF和Tol中配成10-5M的溶液,测试其溶液和薄膜的光致发光光谱。图4为dfpypy-4-PTZ溶液和和薄膜的光致发光光谱,图5为(dfpypy-4-PTZ)2IrPic溶液及其薄膜的光致发光光谱,图6为(dfpypy-4-PTZ)2Ir(pytz)溶液及其薄膜的光致发光光谱。
由图4可知,配体dfpypy-4-PTZ分别在DCM、THF、Tol和薄膜的最大发射峰值分别为583nm、570nm、526nm和513nm,随着溶剂的极性增大,其光致发光光谱发生显著的位移红移。固体薄膜的光致发光光谱蓝移,与镶接的“蝴蝶”结构和C^N配体骨架的非平面性有关。
由图5可知,在光激发下,配合物(dfpypy-4-PTZ)2IrPic发射了宽光谱,配合物在
DCM、THF、Tol溶液和薄膜中的最大发射峰值分别为614nm、583nm、583nm和547 nm,其色坐标分别在(0.56,0.41)、(0.44,0.43)、(0.51,0.48)和(0.35,0.46),很明显,(dfpypy-4-PTZ)2IrPic薄膜出现了暖白光发射。
由图6可知,在光激发下,配合物(dfpypy-4-PTZ)2Ir(pytz)也发射了宽光谱,配合物在 DCM、THF、Tol溶液和薄膜中的最大发射峰值分别为622nm、622nm、594nm和 561nm,其色坐标分别在(0.59,0.40)、(0.59,0.40)、(0.53,0.43)和(0.36,0.45),(dfpypy-4- PTZ)2Ir(pytz)薄膜也出现了暖白光发射
将配合物(dfpypy-4-PTZ)2Ir(pytz)以质量分数为10%、15%和20%分别掺杂在聚苯乙烯 (PS)中,测试其掺杂薄膜的光致发光光谱,如图7所示。
由图7可知,在光激发下,配合物(dfpypy-4-PTZ)2Ir(pytz)掺杂PS薄膜,均可获得宽光谱发射,当质量分数为10%、15%、20%和纯配合物薄膜时,色坐标分别为(0.26,0.32)、 (0.29,0.36)、(0.33,0.41)和(0.36,0.45)。很明显,当掺杂浓度为15%时,掺杂薄膜得到的色坐标和标准白光坐标(0.33,0.33)最为接近。
实施例4
实施例1中的配合物(dfpypy-4-PTZ)2IrPic和(dfpypy-4-PTZ)2Ir(pytz)的单晶结构测试。
配合物(dfpypy-4-PTZ)2IrPic和(dfpypy-4-PTZ)2Ir(pytz)的单晶在二氯甲烷/甲醇混合溶剂体系中培养得到,分别如图8所示、图9所示。
由图8可以发现,配合物(dfpypy-4-PTZ)2IrPic呈八面体结构。铱原子与主配体dfpypy- 4-PTZ配位键长为2.0412.0652.009和1.986 与辅助配体Pic的配位键长为2.137和2.145
由图9可以发现,配合物(dfpypy-4-PTZ)2Ir(pytz)呈八面体结构。铱原子与主配体 dfpypy-4-PTZ配位键长为2.0622.0611.989和1.987与辅助配体pytz的配位键长为2.125和2.164
尽管结合了优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解所附权利要求概括了本发明的范围。在本发明构思的指导下,本领域的技术人员应当意识到,对本发明的各实施例方案所进行的一定的改变,都将被本发明的权利要求书的精神和范围所覆盖。
Claims (4)
4.如权利要求1或2所述的环金属铱配合物单分子白光材料的应用,其特征在于:通过调节溶剂的极性或掺杂薄膜中聚苯乙烯的质量分数,实现环金属铱配合物的溶液或掺杂聚苯乙烯薄膜中的单分子白光发射。
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