S-shaped para-Quinodimethane-Embedded Double [6]Helicene and Its Charged Species Showing Open-Shell Diradical Character.

diradicaloid helicenes isomerization polycycles quinodimethanes

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
01 Dec 2020
Historique:
received: 19 06 2020
pubmed: 3 7 2020
medline: 3 7 2020
entrez: 3 7 2020
Statut: ppublish

Résumé

Helicenes and extended helical π-conjugated compounds have been widely studied, but most of the systems contain only aromatic benzene or heterocyclic rings, showing local aromatic character. Herein, new S-shaped double [6]helicene 1, which has two embedded para-quinodimethane (p-QDM) units, is reported. Due to the existence of a proaromatic quinoidal substructure, it has open-shell diradical character. Its model compound, C-shaped single [6]helicene 2 containing one p-QDM unit, was also synthesized and compared. Their ground-state structures and electronic properties were systematically studied by a combination of various experimental methods assisted by theoretical calculations. Compound 1 has a double-helical structure in the crystal, with the two terminal [6]helicene units bent in opposite directions (i.e., anti form). However, an anti/syn isomerization process with a moderate interconversion energy barrier was observed on the NMR timescale. Compound 1 shows amphoteric redox behavior. It also exhibits open-shell diradical character (y

Identifiants

pubmed: 32614108
doi: 10.1002/chem.202002952
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

15613-15622

Subventions

Organisme : Ministry of Education, Singapore
ID : R-143-000-692-114, MOE2018-T2-1-152, MOE2014-T3-1-004
Organisme : Ministry of Education, Singapore
ID : R-143-000-B62-114, MOE2018-T2-1-152, MOE2014-T3-1-004

Informations de copyright

© 2020 Wiley-VCH GmbH.

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Auteurs

Qing Jiang (Q)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Yi Han (Y)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Ya Zou (Y)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Hoa Phan (H)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Liu Yuan (L)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Tun Seng Herng (TS)

Department of Materials Science and Engineering, National University of Singapore, 119260, Singapore, Singapore.

Jun Ding (J)

Department of Materials Science and Engineering, National University of Singapore, 119260, Singapore, Singapore.

Chunyan Chi (C)

Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.

Classifications MeSH