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Theoretical investigation into the coordination of R ‐/ S ‐asymmetric uranyl–salophens containing six‐membered ring lactam with cis −/ trans ‐cyclohexylamines
Author(s) -
Yang LiangLiang,
Kong XiangHe,
Wu ZhiLin,
Lin YingWu,
Liao LiFu,
Nie ChangMing
Publication year - 2018
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4387
Subject(s) - chemistry , steric effects , uranyl , ring (chemistry) , stereochemistry , cis–trans isomerism , coordination complex , metal , ion , organic chemistry
A six‐membered ring lactam derivative was introduced in a parallel manner into uranyl–salophens with R / S configuration ( R ‐/ S ‐AUSRLs), which were used as receptors to coordinate with guests of cis −/ trans ‐methylcyclohexylamines ( cis −/ trans ‐MCHAs). Using density functional theory calculations at the B3LYP/6‐311G** level and RECP, an insight into the coordination complexes of the R ‐/ S ‐AUSRLs with cis −/ trans ‐MCHAs was obtained. The results showed that the U atoms of receptors could coordinate with the N atoms of four kinds of cis −/ trans ‐1,2 or − 1,4 guests, but the two kinds of cis −/ trans ‐1,3 guests could not be converged by the same method in the process of structural optimization due to steric hindrance, and thus the cis −/ trans ‐1,3 guests could not be coordinated with the R ‐/ S ‐AUSRLs. The mode of coordination of the R ‐/ S ‐AUSRLs with the guests displayed a significant difference. And the change of R ‐AUSRL coordination ability to the cis −/ trans ‐MCHAs was very large, but that of S ‐AUSRL was small. Overall, the stability of the R ‐series coordination complexes was higher than that of the corresponding S ‐series coordination complexes, and the R ‐AUSRL receptor had better coordination selectivity and higher molecular recognition to the cis −/ trans ‐MCHA guests than the S ‐AUSRL receptor. However, the coordination ability of S ‐AUSRL with the cis −/ trans ‐MCHAs was stronger than that of R ‐AUSRL. It was expected that these results could provide insightful information and theoretical guidance for understanding the molecular recognition of R ‐/ S ‐AUSRLs for cis −/ trans ‐type cyclohexylamine derivatives.