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Intramolecular π-π Interactions in Flexibly Linked Partially Fluorinated Bisarenes in the Gas Phase.

Authors :
Blomeyer S
Linnemannstöns M
Nissen JH
Paulus J
Neumann B
Stammler HG
Mitzel NW
Source :
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2017 Oct 16; Vol. 56 (43), pp. 13259-13263. Date of Electronic Publication: 2017 Sep 19.
Publication Year :
2017

Abstract

Three compounds with phenyl and pentafluorophenyl rings bridged by (CH <subscript>2</subscript> ) <subscript>3</subscript> and (CH <subscript>2</subscript> ) <subscript>2</subscript> SiMe <subscript>2</subscript> units were synthesized by hydrosilylation and C-C coupling reactions. Their solid-state structures are dominated by intermolecular π stacking interactions, primarily leading to dimeric or chain-type aggregates. Analysis of free molecules in the gas phase by electron diffraction revealed the most abundant conformer to be significantly stabilized by intramolecular π-π interactions. For the silicon compounds, structures characterized by σ-π interactions between methyl and pentafluorophenyl groups are second lowest in energy and cannot be excluded completely by the gas electron diffraction experiments. C <subscript>6</subscript> H <subscript>5</subscript> (CH <subscript>2</subscript> ) <subscript>3</subscript> C <subscript>6</subscript> F <subscript>5</subscript> , in contrast, is present as a single conformer. The gas-phase structures served as a reference for the evaluation of a series of (dispersion-corrected) quantum-chemical calculations.<br /> (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Details

Language :
English
ISSN :
1521-3773
Volume :
56
Issue :
43
Database :
MEDLINE
Journal :
Angewandte Chemie (International ed. in English)
Publication Type :
Academic Journal
Accession number :
28834050
Full Text :
https://doi.org/10.1002/anie.201707716