Studies on the Bridge Dependence of Bis(triarylamine) Diradical Dications: Long-Range π-Conjugation and π-π Coupling Systems.

J Org Chem

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures , Nanjing University, Nanjing 210023 , China.

Published: April 2018

Three bis(triarylamine) dications bridged with 2,2'-bithienyl group (1), biphenyl group (2) and [2,2]paracyclophane (3) have been successfully isolated. The electronic structures of 1 - 3 show bridge dependence. Magnetic studies and DFT calculations show that dications 1 - 3 possess an open-shell singlet ground state with a thermally excited triplet state. Dication 3 has rather small singlet-triplet energy gap and could basically be regarded as a nearly pure diradical. Diradical dications 1 - 3 represent rare examples of diradicaloids with intramolecular long-range π-conjugation or π-π coupling interaction.

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http://dx.doi.org/10.1021/acs.joc.8b00003DOI Listing

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