Issue 35, 2012
From the journal:

Dalton Transactions

Novel polyoxometalate hybrids consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments†

Junwei Zhao,ab   Dongying Shi,a   Lijuan Chen,*ac   Yanzhou Li,a   Pengtao Ma,a   Jingping Wanga  and  Jingyang Niu*a  

* Corresponding authors

a Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China
E-mail: zhaojunwei@henu.edu.cn, jyniu@henu.edu.cn
Fax: (+86) 378 3886876

b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China

c Basic Experiment Teaching Center, Henan University, Kaifeng, Henan 475004, P. R. China

Abstract

Three organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates, {[Cu(en)2(H2O)] [Cu3Eu(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (1), {[Cu(en)2(H2O)][Cu3Tb(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (2) and {[Cu(en)2(H2O)][Cu3Dy(en)3(OH)3(H2O)2](α-GeW11O39)}2·10H2O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper–ethylendiamine complexes, Na2H6[Cu(en)2(H2O)]8{Cu(en)2[La(α-GeW11O39)2]2}·18H2O (4), K4H2[Cu(en)2(H2O)2]5[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Pr(α-GeW11O39)2]2}·16H2O (5) and KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Er(α-GeW11O39)2]2}·15H2O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1–3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu3Ln(en)3(OH)3(H2O)2](α-GeW11O39)}24−, which is constructed from two {Cu3LnO4} cubane anchored monovacant [α-GeW11O39]8− fragments through two W–O–Ln–O–W linkers. The primary backbones of 4–6 exhibit the tetrameric architecture {Cu(en)2[Ln(α-GeW11O39)2]2}24− built by two 1 : 2-type [Ln(α-GeW11O39)2]13− moieties and one [Cu(en)2]2+ bridge, albeit they are not isostructural. To our knowledge, 1–6 are rare polyoxometalate derivatives consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu3EuO4} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the TbIII/DyIII and CuII cations. The room-temperature solid-state photoluminescence properties of 1–3 have been investigated.

Graphical abstract: Novel polyoxometalate hybrids consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments

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Article information

DOI
https://doi.org/10.1039/C2DT30949A
Article type
Paper
Submitted
02 May 2012
Accepted
16 Jul 2012
First published
17 Jul 2012

Dalton Trans., 2012,41, 10740-10751

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Novel polyoxometalate hybrids consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments

J. Zhao, D. Shi, L. Chen, Y. Li, P. Ma, J. Wang and J. Niu, Dalton Trans., 2012, 41, 10740 DOI: 10.1039/C2DT30949A

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