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Linear σ‐Hole Bonding Dimers and Trimers Between Dihalogen Molecules XY (X, Y=Cl, Br) and Carbon Monoxide
Author(s) -
Yang Xing,
Yan ChaoXian,
Yang Fan,
Zhou DaGang,
Zhou PanPan,
Liu Shubin
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201700075
Subject(s) - trimer , intermolecular force , cooperativity , dimer , halogen bond , halogen , crystallography , chemistry , molecule , carbon monoxide , counterpoise , linear molecular geometry , hydrogen bond , alkyl , biochemistry , organic chemistry , basis set , catalysis
Intermolecular interactions between CO and dihalogen molecules XY (X, Y=Cl, Br) were investigated at MP2/aug‐cc‐pVDZ level without and with counterpoise method, and single point calculations at CCSD(T)/aug‐cc‐pVDZ level were performed. XY can interact with one or two CO to form linear σ‐hole bonding dimer or trimer. Their optimized geometries, stretching modes and interaction energies were investigated. The X⋅⋅⋅C (or Y⋅⋅⋅C) interaction is stronger and more competitive than X⋅⋅⋅O (or Y⋅⋅⋅O) interaction, so the OC⋅⋅⋅X−Y⋅⋅⋅CO complex is stronger and more competitive than the CO⋅⋅⋅X−Y⋅⋅⋅OC complex. The interaction strengths of trimeric complexes are dependent upon the property of XY, andthe anticooperative or diminutive effects were observed for them. Electrostatic interaction is the dominant net driving force for the formation of these dimers based on EDA analysis. The formation of two linear halogen bonds in each trimer was identified by bond paths and green circle isosurfaces appearing between the halogen and C (or O) atoms. The results would provide valuable insight into the competition and cooperativity of linear halogen bonds.