π-Pimer,π-Dimer,π-Trimer,and 1Dπ-Stacks in a Series of Benzene Triimide Radical Anions:Substituent-Modulated π Interactions and Physical Properties in Crystalline State  

作　　者：De-Hui Tuo Shuxuan Tang Pengfei Jin Jikun Li Xinping Wang Chuang Zhang Yu-Fei Ao Qi-Qiang Wang De-Xian Wang 

机构地区：[1]BeijingNational Laboratory for Molecular Sciences,CASKey Laboratory of MolecularRecognition andFunction,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190 [2]University of Chinese Academy of Sciences,Beijing 100049 [3]State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Collaborative Innovation Center of Advanced Microstructures,Nanjing University,Nanjing 210023 [4]Beijing National Laboratory for Molecular Sciences,Key Laboratory of Photochemistry,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190

出　　处：《CCS Chemistry》2023年第6期1343-1352,共10页中国化学会会刊（英文）

基　　金：This research was supported by the National Natural Science Foundation of China(no.91956126);Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202002 and BMS Junior Fellow Scholarship);China Postdoctoral Science Foundation(no.2020TQ0326).

摘　　要：We herein present the efficient syntheses,crystal structures,and physical properties of a series of novel benzene triimide(BTI)radical anions,emphasizing the relationship between molecular structure with spin–spin intermolecular interactions and physical properties in the crystalline state.BTI radical crystals were preparedby reducingvarious substitutedBTIs(1)with cobaltocene(CoCp2),followed by sequential crystallization processes.Two isolable radical species,that is,neutral molecule-radical anion pair(2)and monoradical species(3),were obtained from BTIs bearing small substituents(ethyl and propyl),while for those bearing larger substituents(butyl,hexyl,and benzyl)sole monoradicals(3)were produced.The radical species showed diverse intermolecular stackings in the crystalline state referred to asπ-pimer,π-dimer,alternatingπ-trimer,and one-dimensional(1D)slippedπ-stacks depending on the length and size of the substituents.Different spin–spin interactions arising from the substituent-tuned radical packings were demonstrated by electron spin resonance(ESR)spectra.The structure–property relationshipwas studied in terms of magnetism and conductivity.The radicalπ-pimers andπ-stacks with effective charge transport exhibited paramagnetic property and conductivity feasibly at room temperature,whileπ-dimers andπ-trimers featuring thermally populated spin-triplet stateswere antiferromagnetic and nonconductive due to their strong radical–radical pairing effect.

关 键 词：radical pimer radical dimer anion radical benzene triimide π-πstacking 

分 类 号：O62[理学—有机化学]