TY - JOUR
T1 - Spectroscopic Evidence for Through-Space Arene-Sulfur-Arene Bonding Interaction in m-Terphenyl Thioether Radical Cations
AU - Monney, Nicolas P.A.
AU - Bally, Thomas
AU - Yamamoto, Takuhei
AU - Glass, Richard S.
N1 - Funding Information:
The authors gratefully acknowledge financial support of this work by the Swiss National Foundation SNF (Grant 200020143410) and the U.S. National Science Foundation NSF (Grant 0956581).
Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/12/31
Y1 - 2015/12/31
N2 - Electronic absorption spectra and quantum chemical calculations of the radical cations of m-terphenyl tert-butyl thioethers, where the S-t-Bu bond is forced to be perpendicular to the central phenyl ring, show the occurrence of through-space [π⋯S⋯π]+ bonding interactions which lead to a stabilization of the thioether radical cations. In the corresponding methyl derivatives there is a competition between delocalization of the hole that is centered on a p-AO of the S atom into the π-system of the central phenyl ring or through space into the flanking phenyl groups, which leads to a mixture of planar and perpendicular conformations in the radical cation. Adding a second m-terphenyl tert-butyl thioether moiety does not lead to further delocalization; the spin and charge remain in one of the two halves of the radical cation. These findings have interesting implications with regard to the role of methionines as hopping stations in electron transfer through proteins.
AB - Electronic absorption spectra and quantum chemical calculations of the radical cations of m-terphenyl tert-butyl thioethers, where the S-t-Bu bond is forced to be perpendicular to the central phenyl ring, show the occurrence of through-space [π⋯S⋯π]+ bonding interactions which lead to a stabilization of the thioether radical cations. In the corresponding methyl derivatives there is a competition between delocalization of the hole that is centered on a p-AO of the S atom into the π-system of the central phenyl ring or through space into the flanking phenyl groups, which leads to a mixture of planar and perpendicular conformations in the radical cation. Adding a second m-terphenyl tert-butyl thioether moiety does not lead to further delocalization; the spin and charge remain in one of the two halves of the radical cation. These findings have interesting implications with regard to the role of methionines as hopping stations in electron transfer through proteins.
UR - http://www.scopus.com/inward/record.url?scp=84952893877&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84952893877&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.5b09665
DO - 10.1021/acs.jpca.5b09665
M3 - Article
C2 - 26636350
AN - SCOPUS:84952893877
SN - 1089-5639
VL - 119
SP - 12990
EP - 12998
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 52
ER -