Assembly of new polyoxometalate–templated metal–organic frameworks based on flexible ligands

Four new polyoxometalate(POM)–templated metal–organic frameworks based on flexible ligands, namely, [Cu6(bip)12(PMoVI12O40)2(PMoVMoVI11O40O2)]·8H2O(1), [CuI3CuII3(bip)12(PMoVI12O40)2(PMoV12O34)]·8H2O(2), [Ni6(bip)12(PMoVI12O40)(PMoVI11MoVO40)2]Cl·6H2O(3), [CoII3CoIII2(H2bib)2(Hbib)2(PW9O34)2(H2O)6]·6H2O(4) (bip=1,3-bis(imidazolyl)propane, bib=1,4-bis(imidazolyl)butane) have been obtained under hydrothermal condition and characterized by single-crystal X-ray diffraction analyses, elemental analyses, and thermogravimetric (TG) analyses. The studies of single crystal X-ray indicate that compounds 1–3 crystallize in the trigonal space group P-3, and compound 4 crystallizes in the triclinic space group P-1. Compounds 1 and 3 represent 3D frameworks, and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals, while compounds 2 and 4 show 3D frameworks by hydrogen bonds. This compounds provide new examples of host–guest compounds based on flexible bis(imidazole) ligands. In addition, the electrochemical property and the catalytic property of compound 1 have also been investigated. Four inorganic–organic hybrid compounds based polyoxometalates (POMs) and flexible ligands, namely, have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1–3 are new examples of host–guest compounds based on flexible bis(imidazole) ligands and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals. [Display omitted] •Polyoxometalate–templated metal–organic frameworks have been prepared.•POMs as the guest molecules are incorporated into the cages.•The cages are flexibility based on flexible bis(imidazole) ligands.