Issue 42, 2009
From the journal:

Dalton Transactions

Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks†

Xiao Zhang,ac   Zhihui Yi,b   Liyan Zhao,a   Qian Chen,a   Xianmo Gu,a   Jiqing Xu,c   Xiaolin Wang,a   Chao Yang,a   Xianzhu Xua  and  Wujiong Xia*a  

* Corresponding authors

a State Key Lab of Urban Water Resource and Environment (SKLUWRE) & Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin, Heilongjiang, P. R. China
E-mail: zhangx@hit.edu.cn, xiawj@hit.edu.cn
Fax: +86 (0)451 8640 3193
Tel: +86 (0)451 8640 3193

b State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P. R China

c College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin, P. R. China

Abstract

Three supramolecular architectures based on α-Keggin-type polyoxometalates have been synthesized hydrothermally, and their structures have been characterized by elemental analyses, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction structure analyses. [Ni(enMe)2(H2O)2]2[Ni(enMe)2PWVI9WV3O40]·H2O (1) (enMe = 1,2′-propanediamine) exhibits a novel 2-D supramolecular sinusoidal layer through the interactions between transition metal complexes and 1-D covalent chains which are constructed from α-Keggin units bridged by transition metal complexes. [Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe)2(H2O)AsWVI6WV4VIV4O42]2}·6H2O (2), representing a 3-D supramolecular framework with 1-D channels, contains the first example of a tungstate dimer with inorganic–organic composite surfaces built up from [Ni(enMe)2]2+ cation bridges and bi-capped α-Keggin polyoxometalate building blocks supporting the transition metal complex. [Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe)2(H2O)AsMoVI4MoV4VIV8O44]2}·8H2O (3), showing a 3-D supramolecular framework with 1-D channels, contains the first example of a molybdoarsenate dimer formed by [Ni(enMe)2]2+ cations bridging two neighboring tetra-capped α-Keggin-based molybdates that support the transition metal complex [Ni(enMe)2H2O]. The topological networks of the supramolecular frameworks of 2 and 3 are analogous. Crystal structural analysis reveals that the dimensionality and the organization of polyoxometalate building units in the solid state can be tuned by the steric hindrances of the polyanions. Both 2 and 3 exhibit intensive photoluminescence.

Graphical abstract: Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

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Article information

DOI
https://doi.org/10.1039/B906313G
Article type
Paper
Submitted
31 Mar 2009
Accepted
17 Aug 2009
First published
03 Sep 2009

Dalton Trans., 2009, 9198-9206

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Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

X. Zhang, Z. Yi, L. Zhao, Q. Chen, X. Gu, J. Xu, X. Wang, C. Yang, X. Xu and W. Xia, Dalton Trans., 2009, 9198 DOI: 10.1039/B906313G

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