Issue 30, 2015

Synthesis and structures of dinuclear cryptates with Zn(ii), Cd(ii) and Hg(ii): tuning the cascade binding mode with metal ions

Abstract

The crystal structures of eight cascade complexes, [Zn2L(μ-Cl)](ClO4)3·2H2O·3CH3CN (1), [Zn2L(μ-Br)](ClO4)3·2H2O·3CH3CN (2), [Cd2L(μ-OH)]2[CdI4]3·6DMF (3), [Cd2L(μ-Cl)][CdCl4](Cl)·4.5H2O (5), [Cd2L(μ-Br)][CdBr4](Br)·1.5H2O (6), [Hg2L(μ-Cl)][HgCl4](Cl)·6H2O (9), [Hg2L(μ-Br)][HgBr4](Br)·1.25H2O (10), and [Hg2L(μ-I)](NO3)3·6H2O (11), were presented, which reveal the influence of the coordinated metal ions on the selectivity in the cascade binding mode. The dizinc(II) cryptate shows the recognition of Cl and Br rather than that of F and I. Unexpectedly, the dicadmium(II) cryptate shows the recognition of OH, F, Cl and Br rather than that of I, while all of the above-mentioned anions can form stable cascade complexes with the dimercury(II) cryptate. For better understanding, the binding behaviors and stabilisation energies between [M2L]4+ and anions were calculated by DFT calculations.

Graphical abstract: Synthesis and structures of dinuclear cryptates with Zn(ii), Cd(ii) and Hg(ii): tuning the cascade binding mode with metal ions

Supplementary files

Article information

Article type
Paper
Submitted
27 Apr 2015
Accepted
21 Jun 2015
First published
08 Jul 2015

CrystEngComm, 2015,17, 5832-5840

Synthesis and structures of dinuclear cryptates with Zn(II), Cd(II) and Hg(II): tuning the cascade binding mode with metal ions

F. Yan, X. Zhuang and T. Lu, CrystEngComm, 2015, 17, 5832 DOI: 10.1039/C5CE00817D

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