基于三苯胺和咔唑的联吡啶铱化合物的合成及其在光催化水产氢中的应用研究  

Synthesis and Photocatalytic Hydrogen Generation of Triphenylamine and Carbazole Based Iridium Bipyridine Complexes

作　　者：郑众 姚思骏 王婷[1] 何卓琳[3] 王启卫[1] ZHENG Zhong;YIU Sze-chun;WANG Ting;HO Cheuk-lam;WANG Qi-wei(Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,China;Department of Chemistry,Hong Kong Baptist University,Hong Kong 000000,China;University of Chinese Academy of Science,Beijing 100049,China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]中国科学院大学,北京100049 [3]香港浸会大学化学系,香港999077

出　　处：《合成化学》2018年第1期1-8,共8页Chinese Journal of Synthetic Chemistry

基　　金：成都市国际科技合作资助(2014-GH02-00014-HZ)

摘　　要：以三苯胺、咔唑、4,4'-二羧基联吡啶为原料,设计并合成了两个联吡啶铱(Ⅲ)配合物Ir1和Ir2,其结构经~1H NMR,^(13)C NMR和HR-MS(MALDI-TOF)表征。并利用紫外可见光谱(UV-Vis)、荧光发射光谱(Photoluminescence)和循环伏安法研究了化合物的光学和电学性质。结果表明:Ir1和Ir2的紫外可见光吸收波长分别位于456 nm和448 nm,相应的发射波长分别为645 nm和678 nm,说明其均能利用可见光;Ir1和Ir2的HOMO电位为-5.125^-5.510 eV,LOMO电位为-2.880^-0.310 eV,满足作为光敏剂的基本条件。研究了化合物在可见光照射下光催化水分解产生氢气的效果。结果表明:Ir1和Ir2的氢气值TONs(turnover numbers)达到2 827和1 908。Two triphenylamine and carbazole based iridium complexes(Ir1,Ir2)with bipyridine molecular framework were designed and synthesized.The structures were characterized by 1 H NMR,13 C NMR and HR-MS(MALDI-TOF).The absorption,photoluminescence and electrochemical properties were studied.The results showed that the maximum absorption wavelength Ir1 and Ir2 extended to 456 nm and 448 nm,respectively.And Ir1 and Ir2 can both fit the basic requirements of photosensitizer in water splitting,with the HOMO and LUMO level of-5.125^-5.51 eV and-2.88^-0.310 eV,respectively.The photocatalytic activities in visible-light driven H 2 production from water in their platinized TiO 2 composites were also studied.A wonderful hydrogen turnover numbers(TONs)of 2 827 and 1 908 were achieved in Ir1 and Ir2 anchored systems respectively.

关 键 词：联吡啶铱 三苯胺 咔唑 合成 光催化产氢 

分 类 号：O621.3[理学—有机化学] O643.3[理学—化学]