Issue 1, 2015

Three multi-nuclear clusters and one infinite chain induced by a pendant 4-butyl-1H-pyrazole ligand for modification of Keggin anions

Abstract

By utilizing pendant 4-butyl-1H-pyrazole (Hbpz) with an alkyl “tail” –(CH2)3CH3, four Keggin-based complexes containing different transition metal multi-nuclear clusters and an infinite chain were hydrothermally synthesized and structurally characterized, [CuI4(bpz)4(pz)2(H6PW11CuIIO39)2]·10H2O (1), [CuII2(bpz)2(H2O)2(H3PCu0.5Mo11.5O40)]·3H2O (2), [Ag3(bpz)2(pz)(H4SiW12O40)]·4H2O (3) and [Ag5(bpz)4(H5/2PMo12O40)2]·6H2O (4) (pz = pyrazole). Compound 1 contains a tetra-nuclear cluster [CuI4(bpz)4(pz)2]2−, in which four CuI ions are fixed by four bpz and two pz ligands. These clusters are linked by Keggin anion dimers to form a 2D layer. In compound 2, the ptz ligands fuse the CuII ions and an infinite 1D metal–organic chain is constructed with the Keggin anions hanging up and down covalently. Compound 3 has a planar triangle tri-nuclear cycle [Ag3(bpz)2(pz)] with three AgI as cores. These cycles build a 3D framework of 3 through the further linkages of Keggin anions and Ag–Ag bonds. In compound 4, there exist discrete [Ag5(bpz)4]+ clusters with four bpz ligands fused by five AgI cores, which are linked by Keggin anions alternately to form a 1D chain. Adjacent chains share the Ag–O bonds and a 2D layer is constructed. The bpz ligand is firstly introduced into the POM field and its successive two N donors are essential for the construction of multi-nuclear clusters and an infinite chain of 1–4. Additionally, the electrochemical and photocatalytic properties of the title compounds have been investigated.

Graphical abstract: Three multi-nuclear clusters and one infinite chain induced by a pendant 4-butyl-1H-pyrazole ligand for modification of Keggin anions

Supplementary files

Article information

Article type
Paper
Submitted
15 Sep 2014
Accepted
27 Oct 2014
First published
03 Nov 2014

Dalton Trans., 2015,44, 386-394

Three multi-nuclear clusters and one infinite chain induced by a pendant 4-butyl-1H-pyrazole ligand for modification of Keggin anions

A. Tian, Y. Ning, J. Ying, X. Hou, T. Li and X. Wang, Dalton Trans., 2015, 44, 386 DOI: 10.1039/C4DT02821J

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