Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical.

Autor: Bonanno NM; Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St.Catharines, Ontario, L2S3A1, Canada., Poddutoori PK; Department of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN, 55812, USA., Sato K; Departments of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan., Sugisaki K; Departments of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan., Takui T; Departments of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.; Research Support Department/University Research Administrator Centre, University Administration Division, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan., Lough AJ; Department of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada., Lemaire MT; Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St.Catharines, Ontario, L2S3A1, Canada.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2018 Oct 09; Vol. 24 (56), pp. 14906-14910. Date of Electronic Publication: 2018 Sep 11.
DOI: 10.1002/chem.201802204
Abstrakt: Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje