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An Interplay of Cooperativity between Cation⋅⋅⋅π, Anion⋅⋅⋅π and CH⋅⋅⋅Anion Interactions
Author(s) -
Mandal Tarun K.,
Samanta Siddhartha,
Chakraborty Sourav,
Datta Ayan
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201300128
Subject(s) - chemistry , cooperativity , ion , fluoride , non covalent interactions , density functional theory , aromaticity , crystallography , crystal structure , cooperative binding , ring (chemistry) , stereochemistry , computational chemistry , inorganic chemistry , hydrogen bond , molecule , binding site , organic chemistry , biochemistry
Abstract Mixed cation (Li + , Na + and K + ) and anion (F − , Cl − , Br − ) complexes of the aromatic π‐surfaces (top and bottom) are studied by using dispersion‐corrected density functional theory. The selectivity of the aromatic surface to interact with a cation or an anion can be tuned and even reversed by the electron‐donating/electron‐accepting nature of the side groups. The presence of a methyl group in the OCH 3 , SCH 3 , OC 2 H 5 in the side groups of the aromatic ring leads to further cooperative stabilization of the otherwise unstable/weakly stable anion⋅⋅⋅π complexes by bending of the side groups towards the anion to facilitate CH⋅⋅⋅anion interactions. The cooperativity among the interactions is found to be as large as 100 kcal mol −1 quantified by dissection of the three individual forces from the total interaction energy. The crystal structures of the fluoride binding tripodal and hexapodal ligands provide experimental evidence for such cooperative interactions.