A series of organic–inorganic hybrids based on lanthanide-substituted Dawson-type phosphotungstate dimers and copper–en linkers†
Abstract
A family of organic–inorganic hybrid monolacunary Dawson phosphotungstate-based TM–Ln hetero-metallic derivatives Na2H(H2en)6[Cu(en)2][LnIII(α2-P2W17O61)2]·men·nH2O (Ln = TbIII, m = 2, n = 26 for 1; Ln = EuIII, m = 2, n = 28 for 2; Ln = SmIII, m = 4, n = 24 for 3; Ln = CeIII, m = 1, n = 21 for 4) (Ln = lanthanide, TM = transition metal, en = 1,2-ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analysis, powder X-ray diffraction (PXRD), IR spectra, thermo-gravimetric (TG) analyses and single-crystal X-ray diffraction. Notably, 1–4 are isomorphic and represent the first family of 1-D chain-like architectures constructed by 1:2-type mono-Ln substituted Dawson-type [LnIII(α2-P2W17O61)]217− dimeric units and [Cu(en)2]2+ connectors, in which the sandwich-type Ln-substituted monolacunary Dawson phosphotungstate fragment is found for the first time in TM–Ln–polyoxotungstate chemistry. Furthermore, the variable-temperature magnetic susceptibility of 1 has been investigated.
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