Stable Quadruple Helical Tetraradicaloid with Thermally Induced Intramolecular Magnetic Switching  

作　　者：Jing Guo Zhiyu Li Jun Zhang Bo Li Yuan Liang Yanpei Wang Sheng Xie Hoa Phan Tun Seng Herng Jun Ding Jishan Wu Ben Zhong Tang Zebing Zeng 

机构地区：[1]State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering/Shenzhen Research Institute,Hunan University,Changsha 410082 [2]School of Materials and Chemical Engineering,Anhui Jianzhu University,Hefei 230039 [3]Jiurui Biotechnology Co.,Ltd.,Zhangjiajie 427000 [4]Department of Chemistry,National University of Singapore,Singapore 117543 [5]Department of Materials Science and Engineering,National University of Singapore,Singapore 119260 [6]Department of Chemistry,Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction,Institute for Advanced Study and HKUST-Shenzhen Research Institute,SCUT-HKUST Joint Research Institute,Hong Kong University of Science and Technology,Hong Kong 999077

出　　处：《CCS Chemistry》2022年第1期95-103,共9页中国化学会会刊（英文）

基　　金：The authors thank the National Natural Science Foundation of China(nos.51922039 and 21671003);the Science and Technology Innovation Program of Hunan Province(no.2020RC5033);the Shenzhen Outstanding Science and Technology Innovation Talent Cultivation Project for financial support.

摘　　要：We report an air-stable tetraradicaloid based on a rarely explored perylenequinonoid(PQ)core,namely,tetrabenzo-annulated tetracyclopenta[b,e,k,n]perylene(TBCP),which has a quadruple helical structure.As validated by X-ray crystallographic analysis and theoretical calculations,the nonplanar TBCP possesses unique hybrid resonance structures of two open-shell singlet diradicaloids.Remarkably,magnetic measurements reveal that TBCP in powder form shows unusual magnetic hysteresis upon heating followed by cooling,corresponding to interconversion of structure isomers with different magnetic properties.Such electronic properties can be rationalized as the response of structural changes to external thermal stimuli,accompanied by a subtle balance of two types of intramolecular magnetic interactions between four-site spin centers.The results provide a novel organic polyradicaloid as an unprecedented example of a functional material with the potential for intramolecular magnetic switching.

关 键 词：polycyclic hydrocarbons polyradicaloid electronic structure singlet-to-triplet energy gap intramolecular magnetic interaction 

分 类 号：O62[理学—有机化学]