Publication
Title
A cryospectroscopic infrared and Raman study of the halogen bonding motif : complexes of the , , and with ethyne, propyne and 2-butyne
Author
Abstract
Experimental information on the Csingle bondX⋯π halogen bonding motif was obtained by studying the formation of molecular complexes of CF3Cl, CF3Br and CF3I with ethyne, propyne and 2-butyne in liquid krypton, using FTIR and Raman spectroscopy. For CF3Br, experimental evidence was found for the formation of 1:1 complexes with propyne and 2-butyne only, while for CF3I spectroscopic features confirming the existence of the halogen bonded complexes were observed for ethyne, propyne and 2-butyne. In addition, at higher concentrations of CF3I and 2-butyne, weak absorptions due to a 2:1 complex were also observed. The experimental complexation enthalpies, obtained by using spectra recorded at temperatures between 120 K and 140 K, are −5.9(3) kJ mol−1 for CF3I.ethyne, −5.6(3) kJ mol−1 for CF3Br.propyne, −8.1(2) kJ mol−1 for CF3I.propyne, −7.3(2) kJ mol−1 for CF3Br.2-butyne, −10.9(2) kJ mol−1 for CF3I.2-butyne and −20.9(7) kJ mol−1 for (CF3I)2.2-butyne. The experimental study is supported by theoretical data obtained from ab initio calculations at the MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) levels, and Monte Carlo Free Energy Perturbation (MC-FEP) simulations. The experimental and theoretical values on the Csingle bondX⋯π halogen-bonding motifs studied are compared with previously reported data for the complexes with ethene and propene and with preliminary results obtained for benzene and toluene.
Language
English
Source (journal)
Spectrochimica acta: part A: molecular and biomolecular spectroscopy. - Oxford
Publication
Oxford : 2015
ISSN
1386-1425
Volume/pages
136:A(2015), p. 16-26
ISI
000347584900003
Full text (Publisher's DOI)
Full text (open access)
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UAntwerpen
Faculty/Department
Research group
Publication type
Subject
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identification
Creation 09.03.2015
Last edited 14.10.2017
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