ONIOM 研究二脲基杯[4]芳烃受体对碱金属配合物阴离子识别。

An ONIOM investigation on anion recognition of alkali-metal complexes with diurea calix[4]arene receptor.

机构信息

Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, Thailand.

出版信息

J Mol Model. 2012 Jun;18(6):2613-20. doi: 10.1007/s00894-011-1284-0. Epub 2011 Nov 13.

PMID:22080288

Abstract

The ONIOM(B3LYP/6-31G(d):AM1) optimized structures of complexes of diurea calix[4]arene receptor (L) with alkali metals Li(+), Na(+) and K(+) and their complexes with halide ions F(-), Cl(-), Br(-), oxygen-containing anions HCO(3)(-), HSO(4)(-) and CH(3)COO(-) ions were obtained. Binding energies and thermodynamic properties of complex receptors LiL(+), NaL(+) and KL(+) with these anions were determined. The binding stabilities according to binding energies of LiL(+), NaL(+) and KL(+) associated with anions computed either at the ZPVE-corrected ONIOM(B3LYP/6-31G(d):AM1) or BSSE-corrected B3LYP/6-31 + G(d,p)//ONIOM(B3LYP/6-31G(d):AM1) are in the same order: F(-) >> CH(3)COO(-) ≈ HCO(3)(-) > Br(-) ≈ HSO(4)(-) ≈ Cl(-). All the receptors LiL(+), NaL(+) and KL(+) were found to be selective toward fluoride ion.

摘要

采用 ONIOM（B3LYP/6-31G(d):AM1）方法优化了二脲基杯[4]芳烃受体（L）与碱金属 Li(+)、Na(+)和 K(+)形成的配合物以及与卤化物 F(-)、Cl(-)、Br(-)、含氧阴离子 HCO(3)(-)、HSO(4)(-)和 CH(3)COO(-)形成的配合物的结构。计算了配合物受体 LiL(+)、NaL(+)和 KL(+)与这些阴离子的结合能和热力学性质。根据 ZPVE 校正的 ONIOM（B3LYP/6-31G(d):AM1）或 BSSE 校正的 B3LYP/6-31 + G(d,p)//ONIOM（B3LYP/6-31G(d):AM1）计算的结合能，LiL(+)、NaL(+)和 KL(+)与阴离子形成的配合物的结合稳定性顺序相同：F(-) >> CH(3)COO(-) ≈ HCO(3)(-) > Br(-) ≈ HSO(4)(-) ≈ Cl(-)。所有的受体 LiL(+)、NaL(+)和 KL(+)都被发现对氟离子具有选择性。