Extended Bis(anthraoxa)quinodimethanes with Nine and Ten Consecutively Fused Six-Membered Rings: Neutral Diradicaloids and Charged Diradical Dianions/Dications

We report the challenging synthesis of two very long bis­(anthraoxa)­quinodimethanes with nine (ABA) and ten (ANA) consecutively fused six-membered rings. The former is stable with negligible diradical character, while the latter with a moderate diradical character (y 0 = 25.0%) is reactive and an u...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2019-01, Vol.141 (1), p.62-66
Main Authors: Dong, Shaoqiang, Gopalakrishna, Tullimilli Y, Han, Yi, Phan, Hoa, Tao, Tao, Ni, Yong, Liu, Gang, Chi, Chunyan
Format: Article
Language:English
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Summary:We report the challenging synthesis of two very long bis­(anthraoxa)­quinodimethanes with nine (ABA) and ten (ANA) consecutively fused six-membered rings. The former is stable with negligible diradical character, while the latter with a moderate diradical character (y 0 = 25.0%) is reactive and an unexpected trifluoroacetic substituted product (ANA-TFA) was isolated. X-ray crystallographic analysis revealed a planar backbone with a typical quinoidal character for both. Their dications can be regarded as the isoelectronic structures of the respective nonacene and decacene. The dication ABA 2+ and dianion ABA 2– are open-shell singlet diradicaloids, while the longer dication ANA-TFA 2+ and dianion ANA 2– have closed-shell ground state, which can be explained by the different intramolecular Coulomb interactions. Both dianions have a bent backbone and can be considered as an isoelectronic structure of the tetraanion of nonacene and decacene, respectively.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b10279