A series of organic–inorganic hybrids based on lanthanide-substituted Dawson-type phosphotungstate dimers and copper–en linkers

• Published in: CrystEngComm 2014-01, Vol.16 (11), p.2230-2238
• Main Authors: Zhao, Hai-Yan, Zhao, Jun-Wei, Yang, Bai-Feng, He, Huan, Yang, Guo-Yu
• Format: Article
• Language: English
• Subjects: Connectors; Derivatives; Diffraction; Dimers; Magnetic permeability; Spectra; Transition metals; X-rays
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/c3ce42029a

A family of organic-inorganic hybrid monolacunary Dawson phosphotungstate-based TM-Ln hetero-metallic derivatives Na sub(2)H(H sub(2)en) sub( 6)[Cu(en) sub(2)][Ln super(III)( alpha sub(2)-P sub(2)W sub(17)O sub(61)) sub(2) .men.nH sub(2)O (Ln = Tb super(III), m= 2, n= 26 for 1; Ln = Eu super(III), m= 2, n= 28 for 2; Ln = Sm super(III), m= 4, n= 24 for 3; Ln = Ce super(III), 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 [Ln super(III)( alpha sub(2)- P sub(2)W sub(17)O sub(61))] sub(2) super(17-) dimeric units and [Cu(en) sub(2)] super(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.