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Long distance structural consequences of H‐bonding: the case of complexes of para ‐substituted phenol derivatives
Author(s) -
Szatyłowicz Halina,
Krygowski Tadeusz M.
Publication year - 2009
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1511
Subject(s) - chemistry , hydrofluoric acid , bond length , phenol , hydrogen bond , proton , fluoride , crystallography , ring (chemistry) , bond strength , binding energy , bond energy , computational chemistry , stereochemistry , molecule , organic chemistry , inorganic chemistry , atomic physics , adhesive , crystal structure , physics , layer (electronics) , quantum mechanics
H‐bonded complexes of p ‐X‐PhOH/ p ‐X‐PhO − with fluoride and hydrofluoric acid (X = OH, H, NO 2 ) were subject of optimization (by means of B3LYP/6‐311+G**) for gradually changed O···F distance from d O···F = 4.0 Å down to (i) the distance of the proton transfer from the hydroxyl group to fluoride leading to O − ···HF interaction and (ii) fully optimized system (O − ···HF type). In this way, we simulate gradual changes of H‐bond strength estimating simultaneously the energy of interaction, E int , energy of deformation, E def , and the binding energy, E tot . The obtained geometrical parameters allow us to show that H‐bond formation causes substantial changes in geometry, even at so distant parts of the system as the ring and bond length in para ‐substituents (OH and NO 2 ). All these changes are monotonically dependent on interaction and deformation energies. Copyright © 2009 John Wiley & Sons, Ltd.