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Intramolecular π–π Interactions in Flexibly Linked Partially Fluorinated Bisarenes in the Gas Phase
Author(s) -
Blomeyer Sebastian,
Linnemannstöns Marvin,
Nissen Jan Hendrick,
Paulus Jannik,
Neumann Beate,
Stammler HansGeorg,
Mitzel Norbert W.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707716
Subject(s) - intramolecular force , intermolecular force , stacking , chemistry , conformational isomerism , hydrosilylation , electron diffraction , crystallography , molecule , gas phase , phase (matter) , diffraction , computational chemistry , stereochemistry , organic chemistry , physics , optics , catalysis
Three compounds with phenyl and pentafluorophenyl rings bridged by (CH 2 ) 3 and (CH 2 ) 2 SiMe 2 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 6 H 5 (CH 2 ) 3 C 6 F 5 , 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.