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Density functional theory study of the free and tetraprotonated spheroidal macrotricyclic ligands and the complexes with halide anions: F − , Cl − , Br −
Author(s) -
Zheng Xiaoyan,
Wang Xueye,
Yi Shanfeng,
Wang Nuanqing,
Peng Yueming
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21352
Subject(s) - chemistry , natural bond orbital , intramolecular force , halide , density functional theory , hydrogen bond , lone pair , crystallography , intermolecular force , computational chemistry , binding energy , molecule , stereochemistry , inorganic chemistry , atomic physics , physics , organic chemistry
Theoretical studies of the macrotricyclic tetramine hexaether (SC), its tetraprotonated form SC‐4H + , and the corresponding complexes X − ⊂SC‐4H + (This expression represents the structural properties of the halide inclusion complex formed though the free ligand SC‐4H + and the halide anion X − : the spherical halide anion X − is held by a tetrahedral array of + NH ··· X − hydrogen bonds inside the intramolecular cavity of the tetraprotonated form SC‐4H + ) of SC‐4H + with the halide anions: F − , Cl − , and Br − have been performed using density functional theory (DFT) with B3LYP/6‐31G method implemented in the Gaussian 03 program package. The optimized geometric structures obtained from DFT calculations are used to perform Natural Bond Orbital (NBO) analysis. The three main types of hydrogen bonds + NH ··· F − , + NH ··· Cl − , and + NH ··· Br − are investigated. The results indicate that hydrogen bonding interactions are dominant and the halide anions: F − , Cl − , and Br − offer lone pair electrons to the contacting σ* (NH) antibond orbital of SC‐4H + . For all the structures, the most pronounced changes in geometric parameters upon interaction are observed in the proton‐donor molecule. The intermolecular interaction energies are predicted by using B3LYP/6‐31G methods with basis set superposition error (BSSE) and zero‐point energy (ZPE) correction. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010