新型咔唑衍生物的合成及发光性能研究  

Synthesis and Luminescent Properties of New Carbazole Derivatives

作　　者：曹建华 李敏 赵雷 韩洪波 田会强 邓师勇 CAO Jian-hua;LI Min;ZHAO Lei;HAN Hong-bo;TIAN Hui-qiang;DENG Shi-yong(Beijing Bayi Space LCD Technology Co.,Ltd.,Beijing 102500,China;Department of Business Administration,Law Business School,China University of Political Science,Beijing 100088,China)

机构地区：[1]北京八亿时空液晶科技股份有限公司,北京102500 [2]中国政法大学商学院工商管理系,北京100088

出　　处：《化学试剂》2022年第2期224-232,共9页Chemical Reagents

摘　　要：基于螺二芴的大位阻结构和咔唑的高三线态能级,设计了一种在咔唑的3、4和5、6位并入两个高位阻的螺二芴结构,以4,4′-二甲基联苯为起始原料,经过硝化反应、Bucherer反应、偶联反应、卤化、Suzuki偶联反应和关环等反应成功制备了咔唑衍生物CzSF2,产物结构经过^(1)HNMR、^(13)CNMR、MS确证。其在二氯甲烷溶液中的最强发射峰位于384 nm,磷光发射峰位于450 nm,CzSF2的E_(S1)和E_(T1)分别为3.4 eV和2.88 eV。以CzSF2和3,3′-二(9-咔唑基)联苯(mCBP)为磷光主体材料,分别掺杂3%、6%和10%的(2-氘甲基-8-(2-吡啶基)苯并呋喃[2,3-b]吡啶)双(2-苯基吡啶)铱(Ⅲ)(GD030)制备了绿色磷光电致发光器件(PhOLEDs),在较低(3%)掺杂浓度下,实现了较高的电流效率、功率效率和外量子效率,分别为98.5 cd/A、83.0 l m/W和25.2%,与mCBP作为主体材料相比,驱动电压低约11%、发光效率高约4%。研究结果表明:利用高度扭曲的螺二芴共轭结构和位阻优势以及高π-π共轭的咔唑设计合成的材料CzSF2具有高的热稳定性、高的三线态能级,非常适用于有机电致发光二极管的发光层,用于磷光主体材料,本征光电性能良好,其设计思路对实现低浓度铱配合物的掺杂具有借鉴意义。Based on the large steric hindrance of spirobifluorene and the high triplet energy level of carbazole,we designed a carbazole derivative,structure of which has two spirobifluorenes at 3,4 and 5,6 positions of carbazole.By using 4,4′-dimethylbiphenyl as starting material,the double 9,9′-spirobifluorenes and one carbazole derivative CzSF2 was synthesized via sequential reactions of nitration,Bucherer reaction,coupling,halogenations,Suzuki-Miyaura coupling,cyclization reaction and other reactions.All compounds were identified by^(1)HNMR,^(13)CNMR and MS spectra.The emission spectrum of CzSF2 showed a maximum peak at 384 nm and the phosphorescence emission peak located at 450 nm at low temperature,therefore,the E_(S1)and E_(T1)were calculated to be 3.4 eV and 2.88 eV,respectively.CzSF2 and mCBP are used as the phosphorescent host materials,and the green phosphorescent organic light-emitting diodes devices(PhOLEDs)were fabricated by doping with 3%,6%and 10%of iridium complex 2-(methyl-d3)-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine)bis[2-phenylpyridinato-C2,N]Ir(Ⅲ)(GD030),respectively.The highest current efficiency,power efficiency and external quantum efficiency were achieved in low(3%)doping concentrations,which were 98.5 cd/A,83.0 l m/W and 25.2%,respectively.Compared with mCBP as the host material,the driving voltage is 11%lower and the luminous efficiency is about 4%higher.These results indicate that the material of CzSF2,designed by taking advantages of the highly twisted spirobifluorene conjugated structure,steric hindrance and the highπ-πconjugated carbazole,has high thermal stability and high triplet energy level,which is suitable for organic electroluminescence.The light-emitting layer of the OLEDs is used as the phosphorescent host material that has good intrinsic photoelectric performance.The design ideas of host material have reference significance to realize the dopant with lower concentrations of iridium complex.

关 键 词：4 4′-二甲基联苯 螺二芴 咔唑 有机电致发光材料 磷光主体材料 

分 类 号：O626.2[理学—有机化学]