Issue 33, 2012

Polynuclear complexes of main group and transition metals with polyaminopolycarboxylate and polyoxometalate

Abstract

Six supramolecular compounds constructed by main group and transition metals, polyoxotungstates (SiW12O404−) and trans-N,N,N′,N′-1,2-cyclohexanediaminotetraacetic acid (H4CyDTA), (NH4)3[Ni4Na(H2O)10(CyDTA)2][SiW12O40]·10H2O (1) (NH4)2[Cu3Na2(HCyDTA)2(H2O)13][SiW12O40]·5H2O (2), (NH4)2[Zn5(CyDTA)2(H2O)16][SiW12O40]·8H2O (3), (NH4)4[Cd4(CyDTA)2(H2O)8][SiW12O40]·6H2O (4), (NH4)4[Sr3(HCyDTA)2(H2O)14][SiW12O40]·2H2O (5) and [Ca4(H2CyDTA)2(H2O)22][SiW12O40]·8H2O (6), were synthesized in aqueous solution and characterized by IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction techniques. Single-crystal structure analyses indicate they are constructed by the complexes with different nuclearity and polyoxometalates. In the sequence of Ni, Cu, Zn the nuclearity of the homometallic complex units increases from 2 to 5. Cadmium ions gives a tetranuclear complex with a compact structure. In 5 and 6 the main group metal ions and CyDTA form polymeric chains. CyDTA exhibits rather different coordination patterns to main group metal ions and transition metal ions due to their ionic radii and electronic configuration. The complex units and polyoxometalates arrange in different patterns due to the different shapes of the complex units. The compounds exhibit different thermal decomposition processes and the formation of compounds 3 and 4 quenches ligand-centered emissions and gives a ligand-to-metal emission. The study on various temperature susceptibilities of 1 and 2 shows that there is an antiferromagnetic coupling in the two compounds but coupling patterns are different.

Graphical abstract: Polynuclear complexes of main group and transition metals with polyaminopolycarboxylate and polyoxometalate

Supplementary files

Article information

Article type
Paper
Submitted
30 Dec 2011
Accepted
15 Mar 2012
First published
16 Mar 2012

Dalton Trans., 2012,41, 9971-9978

Polynuclear complexes of main group and transition metals with polyaminopolycarboxylate and polyoxometalate

C. Zhang, Y. Chen, Q. Tang and S. Liu, Dalton Trans., 2012, 41, 9971 DOI: 10.1039/C2DT12508K

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