Wang Lei, Zhang Li, Fang Yong, Zhao Yue, Tan Gengwen, Wang Xinping
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
Chem Asian J. 2019 May 15;14(10):1708-1711. doi: 10.1002/asia.201801816. Epub 2019 Mar 6.
Two bis(triarylamine) diradical dication salts 1 2[Al(OR ) ] and 2 2[Al(OR ) ] bridged with an orthogonal oriented bisanthrancene motif were synthesized. Their solid state and electronic structures were investigated by various experimental approaches in conjunction with theoretical calculations. Superconducting quantum interference device measurements and density functional theory calculations reveal that both of 1 and 2 feature open-shell singlet ground states with rather small singlet-triplet energy gaps; thus, they can be regarded as nearly pure diradicals (biradicals). Their diradical characters are enhanced by the orthogonal configuration of the bisanthrancene moiety which demonstrates the importance of the geometry of bridging units in turning the electronic structures of bis(triarylamine) dications.
合成了两种由正交取向的双蒽基序桥联的双（三芳基胺）双自由基双阳离子盐1 2[Al(OR ) ]和2 2[Al(OR ) ]。通过各种实验方法结合理论计算对它们的固态结构和电子结构进行了研究。超导量子干涉装置测量和密度泛函理论计算表明，1和2都具有开壳单重基态，单重态-三重态能隙相当小；因此，它们可被视为近乎纯粹的双自由基。双蒽部分的正交构型增强了它们的双自由基特性，这证明了桥联单元的几何结构在改变双（三芳基胺）双阳离子电子结构方面的重要性。
