Nitrogen-bridged Ni(Ⅱ)porphyrinoid trimers with a central quinodiimine unit  

作　　者：Kaisheng Wang Boyu Xiao Ling Xu Mingbo Zhou Takayuki Tanaka Atsuhiro Osuka Jianxin Song 

机构地区：[1]College of Chemistry and Chemical Engineering,Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research(Ministry of Education of China),Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province,Hunan Normal University,Changsha 410081,China [2]Department of Chemistry,Graduate School of Science Kyoto University,Kyoto 606-8502,Japan

出　　处：《Chinese Chemical Letters》2022年第10期4545-4548,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21772036,22071052,21602058,21702057);the Science and Technology Planning Project of Hunan Province(No.2018TP1017);the Scientific Research Fund of Hunan Provincial Education Department(No.19A331);Hunan Provincial Innovation Foundation for Postgraduate(No.CX20210473)。

摘　　要：Buchwald-Hartwig amination of 5,15-dibromo and 5,10-dibromo Ni(Ⅱ)porphyrins with 5-amino Ni(Ⅱ)porphyrin gave linear and bent trimers 4Ni and 5Ni with a central quinodiimine-type Ni(Ⅱ)porphyrinoid.The structures of 4Ni and 5Ni have been confirmed by X-ray diffraction analysis in both cases.The formation of unusual products 4Ni and 5Ni has been ascribed to facile oxidation of 5,15-and 5,10-amino Ni(Ⅱ)porphyrin unit.Reduction of 4Ni and 5Ni under proper conditions gave NH-bridged Ni(Ⅱ)porphyrin trimers 4Ni-2H and 5Ni-2H in high yields.Trimers 4Ni and 5Ni exhibit the lowest energy band as compared with 4Ni-2H and 5Ni-2H.Especially the bent trimer 5Ni exhibits a broad absorption tail beyond 1400 nm.

关 键 词：Porphyrinoid trimer Aminoporphyrins Buchwald-Hartwig amination Reduction Charge transfer 

分 类 号：O641.3[理学—物理化学]