Conformation Governed Reactivity of Fused Thia-Sapphyrin Dimers Bearing Multiply Fused Heteroaromatic Rings  

作　　者：Qizhao Li Masatoshi Ishida Chengjie Li Glib Baryshnikov Feng Sha Bin Zhu Xinyan Wu HansÅgren Hiroyuki Furuta Yongshu Xie 

机构地区：[1]Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering,Feringa Nobel Prize Scientist Joint Research Center,Frontiers Science Center for Materiobiology and Dynamic Chemistry,Institute of Fine Chemicals,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237 [2]Department of Chemistry,Graduate School of Science,Tokyo Metropolitan University,Tokyo 192-0397 [3]Department of Science and Technology,Laboratory of Organic Electronics,Linköping University,Norrköping SE-60174 [4]Department of Physics and Astronomy,Uppsala University,Uppsala SE-75120 [5]Department of Applied Chemistry,Graduate School of Engineering,Kyushu University,Fukuoka 819-0395 [6]Research Organization of Science and Technology,Ritsumeikan University,Kusatsu 525-8577

出　　处：《CCS Chemistry》2023年第6期1332-1342,共11页中国化学会会刊（英文）

基　　金：The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for compound characterization.

摘　　要：Suitable conformations and proper alignment of complex natural macrocycles are essential for achieving their unique properties.However,such artificial macrocycle prototypes are still limited due to synthetic difficulties.In this respect,directly linked porphyrin analog dimers display tunable conformations and intriguing properties,and thus,they may be employed as a class of promising platforms.Herein,we report that one-pot oxidative dimerization of thiahydrosapphyrin 1 yields dimers,2anti and 2syn,comprising a transoid-oriented plate-like bipyrrolo[1,2-a]indolylidene.The thiophene-containing tetrapyrrole arching subunits in 2 lie at the opposite(anti)and same(syn)sides of the plate,respectively.Meanwhile,multiply fused cisoid-orientated dimer 3 was also obtained;a polycyclic pyrrolo-bridged bipyrroloindole derivative tethered with fullyπ-conjugated bridges was formed.Notably,the anti-dimer 2anti underwent subsequent oxidative fusion to furnish a further-fused[6.5.5.7.5.5.5.6]-octacyclic compound 4anti.In contrast,the syn-orientated 2syn could not be further fused due to the long distance between the potential reaction sites.This study provides a unique approach to the fused dimeric porphyrin analogs for potential near-infrared optical materials by a simple oxidation reaction.It also reveals the importance of conformation-modulated reactivity for constructing complex porphyrin arrays.

关 键 词：PORPHYRINS PORPHYRINOIDS sapphyrins π-conjugated systems porphyrin oligomers nearinfrared dyes macrocycles 

分 类 号：O62[理学—有机化学]