Cyclobis(7,8-(para-quinodimethane)-4,4′-triphenylamine) and Its Cationic Species Showing Annulene-Like Global (Anti)Aromaticity
Dr. Shaoqiang Dong
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Tullimilli Y. Gopalakrishna
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorCorresponding Author
Prof. Chunyan Chi
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Shaoqiang Dong
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Tullimilli Y. Gopalakrishna
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorCorresponding Author
Prof. Chunyan Chi
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorAbstract
π-Conjugated macrocycles containing all-benzenoid rings usually show local aromaticity, but reported herein is the macrocycle CBQT, containing alternating para-quinodimethane and triphenylamine units displaying annulene-like anti-aromaticity at low temperatures as a result of structural rigidity and participation of the bridging nitrogen atoms in π-conjugation. It was easily synthesized by intermolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. X-ray crystallographic structures of CBQT, as well as those of its dication, trication, and tetracation were obtained. The dication and tetracation exhibited global aromaticity and antiaromaticity, respectively, as confirmed by NMR measurements and theoretical calculations. Both the dication and tetracation possess open-shell singlet ground states, with a small singlet–triplet gap.
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