title: pH-controlled and sulfite anion-directed assembly of a family of cerium(III)-containing polyoxotungstates clusters.
abstract: A versatile one-pot strategy was employed to synthesize five cerium(III)-containing polyoxotungstate nanoclusters through pH-controlled and sulfite anion-directed assembly: [C2H8N]3Na7[Ce2(H2O)6W22O72(OH)4]·20H2O (1) at pH 5.0; [C2H8N]8Na16[Ce4(H2O)12W44O144(OH)12]·23H2O (2) at pH 4.5; [C2H8N]2Na4Ce2[Ce2(H2O)10W28O92(OH)2]·27H2O (3) at pH 2.8-3.3; [C2H8N]2Na7[{α-SW7O28}{Ce2(H2O)6}(W3O6){α-SW9O32}{α-SW9O31(OH)}]·18H2O (4) at pH 2.5; [C2H8N]2Na18[Ce2(H2O)9W36O110(OH)12]2·30H2O (5) at pH 1.5. These compounds were characterized by single-crystal X-ray structure analysis, IR spectroscopy, thermogravimetric (TG) analysis, X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Moreover, their electrochemical properties were investigated. Single-crystal X-ray structure analysis revealed that 1 and 2 were di- and tetra-cerium(III)-bridged polyoxotungstates, constructed from two different types of lacunary {W11} units. 3 composed of the well-known cerium(III)-stabilized {W28} unit and organic amine-sodium-cerium cations, was isolated in the pH range 2.8-3.3. In this reaction system, the SO3(2-) anion acted as a heteroanion template at a lower pH 2.5. 4 was isolated by the combination of cerium(III) centers and SO3(2-) heteroanion template, which is the first lanthanide-containing polyoxotungstates with sulfur heteroatoms, and the 4f metal cerium(III) centers in 4 both have eight-coordinated modes and the SO3(2-) heteroanion templates display μ7 and μ9 coordination modes. At a much lower pH 1.5, the polyanion of 5 was obtained, two triangular-shaped {W36} subunits were bridged by the cerium(III) ions, resulting in the largest lanthanide-containing iso-polyoxotungstates known to date.
authors.affiliation: Department Institute of Functional Material Chemistry, Key Lab of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University , Changchun 130024, P. R. China.
authors.forename: Wei-Chao
authors.initials: WC
authors.lastname: Chen
authors.forename: Xin-Long
authors.initials: XL
authors.lastname: Wang
authors.forename: Yan-Qing
authors.initials: YQ
authors.lastname: Jiao
authors.forename: Peng
authors.initials: P
authors.lastname: Huang
authors.forename: En-Long
authors.initials: EL
authors.lastname: Zhou
authors.forename: Zhong-Min
authors.initials: ZM
authors.lastname: Su
authors.forename: Kui-Zhan
authors.initials: KZ
authors.lastname: Shao