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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Wang, Jingping Shi, Dongying Chen, Lijuan Zhao, Junwei Ma, Pengtao Li, Yanzhou Niu, Jingyang
Description	Author Affiliation: Zhao J ( Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PR China. zhaojunwei@henu.edu.cn)
Abstract	Three organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates, $\{[Cu(en)_{2}(H_{2}O)]$ $[Cu_{3}Eu(en)_{3}(OH)_{3}(H_{2}O)_{2}](α-GeW_{11}O_{39})\}_{2}·11H_{2}O$ (1), $\{[Cu(en)_{2}(H_{2}O)][Cu_{3}Tb(en)_{3}(OH)_{3}(H_{2}O)_{2}](α-GeW_{11}O_{39})\}_{2}·11H_{2}O$ (2) and $\{[Cu(en)_{2}(H_{2}O)][Cu_{3}Dy(en)_{3}(OH)_{3}(H_{2}O)_{2}](α-GeW_{11}O_{39})\}_{2}·10H_{2}O$ (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper– ethylendiamine complexes, $Na_{2}H_{6}[Cu(en)_{2}(H_{2}O)]_{8}\{Cu(en)_{2}[La(α-GeW_{11}O_{39})_{2}]_{2}\}·18H_{2}O$ (4), $K_{4}H_{2}[Cu(en)_{2}(H_{2}O)_{2}]_{5}[Cu(en)_{2}(H_{2}O)]_{2}[Cu(en)_{2}]_{2}\{Cu(en)_{2}[Pr(α-GeW_{11}O_{39})_{2}]_{2}\}·16H_{2}O$ (5) and $KNa_{2}H_{7}[enH_{2}]_{3}[Cu(en)_{2}(H_{2}O)]_{2}[Cu(en)_{2}]_{2}\{Cu(en)_{2}[Er(α-GeW_{11}O_{39})_{2}]_{2}\}·15H_{2}O$ (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 $\{[Cu_{3}Ln(en)_{3}(OH)_{3}(H_{2}O)_{2}](α-GeW_{11}O_{39})\}_{2}^{4−},$ which is constructed from two $\{Cu_{3}LnO_{4}\}$ cubane anchored monovacant $[α-GeW_{11}O_{39}]^{8−}$ fragments through two W–O–Ln–O–W linkers. The primary backbones of 4–6 exhibit the tetrameric architecture $\{Cu(en)_{2}[Ln(α-GeW_{11}O_{39})_{2}]_{2}\}^{24−}$ built by two 1:2-type $[Ln(α-GeW_{11}O_{39})_{2}]^{13−}$ 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 $\{Cu_{3}EuO_{4}\}$ cubane units, while 2 and 3 display dominant ferromagnetic interactions between the $Tb^{III}/Dy^{III}$ and $Cu^{II}$ cations . The room-temperature solid-state photoluminescence properties of 1–3 have been investigated.
ISSN	14779226
Issue Number	35
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-09-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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