Cooperative effects in FH/Li⋯HCCX⋯OH2 complexes (X=F, Cl, Br, H).
The dimers with general formula FH/FLi⋯HCCX and HCCX⋯OH2, and the trimers FH⋯HCCX⋯OH2 (X=F, Cl, Br, H), were optimized computationally to stable structures. These model systems derive their strength from a combination of H⋯π (or Li⋯π) electrostatic interactions in the T-shaped FH/FLi⋯HCCX dimers and halogen bonding between the X and the O atom of H2O (or CH⋯O hydrogen-bonding in HCCH complexes). These cooperative interactions in the trimer clusters yield a non-additive energy which enhances the stability by between 7% and 10%. The variation in the interaction energies, as well as other selected properties, for different X is rationalized and discussed.
Department of Biological and Chemical Sciences, The University of the West Indies, Cave Hill Campus, Barbados. Electronic address: sacm@mail.com.
Sean A C
SA
McDowell
Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
A David
AD
Buckingham
D000480:Alkynes / Q000737:chemistry; D019281:Dimerization; D005459:Fluorides / Q000737:chemistry; D006219:Halogens / Q000737:chemistry*; D006858:Hydrofluoric Acid / Q000737:chemistry; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D018020:Lithium Compounds / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D055672:Static Electricity
D000480:Alkynes; D006219:Halogens; D018020:Lithium Compounds; C027651:lithium fluoride; D008094:Lithium; D005459:Fluorides; D006858:Hydrofluoric Acid
Cooperative effect; Halogen bond; Hydrogen bond; Lithium bond