Light-and Heat-Controlled Formation of Osmanaphthalenes and Osmanaphthalynes  

作　　者：Ming-Xing Zhang Xiaofei Yang Zhiqiang Xu Jun Yin Sheng Hua Liu 

机构地区：[1]Key Laboratory of Pesticide and Chemical Biology,Ministry of Education,College of Chemistry,Central China Normal University,Wuhan,Hubei,430079 China [2]Hubei Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients,College of Chemistry and Life Science,Hubei University of Education,Wuhan,Hubei,430205 China [3]Key Laboratory for Green Chemical Process of Ministry of Education,School of Chemical Engineering and Pharmacy,Wuhan Institute of Technology,Wuhan,Hubei,430205 China

出　　处：《Chinese Journal of Chemistry》2022年第24期2853-2860,共8页中国化学（英文版）

基　　金：support from the National Natural Science Foundation of China(22175069 and 21772054);the 111 Project(B17019);the Natural Science Foundation of Hubei Province,China(2020CFB227);the Foundation of Hubei Provincial Department of Education(grant no.B2020173).

摘　　要：mple and efficient synthesis of metalla-aromatics with tailored distinctive optical,magnetic,redox,and light-emitting properties is attractive yet challenging.We have now successfully synthesized three paramagnetic osmanaphthalenes bearing different electron-donating groups as well as the first osmabenzo[b]carbazole containing an osmanaphthalene unit with four fused rings in good yields by subjecting suitable osmium carbyne precursors to a visible-light-induced protocol.In contrast,the four corresponding diamagnetic cyclic metal carbynes containing an osmanaphthalyne unit were obtained from the same osmium carbyne precursors by a heating method.The lowest-energy absorptions of the paramagnetic osmanaphthalenes are red-shifted compared to the corresponding osmanaphthalynes.Additionally,experimental observations including X-ray analysis as well as nucleus-independent chemical shift(NICS),anisotropy of the current-induced density(AICD)calculations revealed these novel osmapolycycles bearing phosphonium substituents to be of aromatic character.

关 键 词：METALLACYCLES AROMATICITY Osmanaphthalyne Osmanaphthalene PHOTOLYSIS 

分 类 号：O61[理学—无机化学]