Synthesis and Properties of a Through-Space Interacting Diradicaloid  

作　　者：Takuya Kodama Yasukazu Hirao Takashi Kubo 

机构地区：[1]Department of Chemistry,Graduate School of Science,Osaka University,Toyonaka,Osaka 560-0043,Japan [2]Innovative Catalysis Science Division,Institute for Open and Transdisciplinary Research Initiatives,(ICSOTRI),Osaka University,Suita,Osaka 565-0871,Japan

出　　处：《Precision Chemistry》2023年第3期183-191,共9页精准化学（英文）

基　　金：the JSPS for KAKENHI funding(Grant No.JP21H01918 and JP20K21194);a Grant-in-Aid for Transformative Research Areas(A)“Condensed Conjugation”(JSPS for KAKENHI funding Grant No.JP20H05865)from MEXT,Japan.

摘　　要：Knowledge about electronic structures is important to gain an understanding of the unique functional properties of diradicaloids.In this study,we synthesized and characterized a diradicaloid in which two phenalenyl radical sites are coupled antiferromagnetically via a through-space interaction.The results of quantum chemical,physicochemical(^(1)H NMR,electronic absorption,cyclic voltammetry,SQUID,ESR),and chemical reactivity studies show that this diradicaloid has singlet diradical character.An assessment of the nature of the bonding interaction between two radical sites in this species using DFT calculations demonstrates that a small spatial overlap between the two SOMOs in this diradicaloid provides an efficient electron exchange path for the singlet state to be substantially lower in energy than the triplet state.

关 键 词：through-space interaction phenalenyl radical singlet diradical diradicaloid antiferromagnetic interaction 

分 类 号：O62[理学—有机化学]