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Issue 30, 2015
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Synthesis and structures of dinuclear cryptates with Zn(II), Cd(II) and Hg(II): tuning the cascade binding mode with metal ions

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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

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Publication details

The article was received on 27 Apr 2015, accepted on 21 Jun 2015, published on 08 Jul 2015 and first published online on 08 Jul 2015


Article type: Paper
DOI: 10.1039/C5CE00817D
Citation: CrystEngComm, 2015,17, 5832-5840
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    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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