화학공학소재연구정보센터
Inorganic Chemistry, Vol.45, No.20, 8036-8040, 2006
Two-dimensional lanthanide heteropolyvanadates of manganese(IV) and nickel(IV) containing two types of heteropoly anions with 1 : 13 and 1 : 12 stoichiometry
Reactions of 1:13 heteropoly anions [MV13O38](7-) (M = Mn, Ni) and lanthanide cations Ln(3+) (Ln = La, Ce, or Pr) produce five isomorphic compounds, which are crystallized in the triclinic crystal system, space group P (1) over bar, and formulated as Ln(6)(H2O)(25)(MV12O38)(HMV13O38)](.)nH(2)O((1)Ln = La, M = Mn, and n approximate to 31; (2) Ln = Ce, M = Mn, and n approximate to 29; (3) Ln = Pr, M = Mn, and n approximate to 31; (4) Ln = La, M = Ni, and n approximate to 28; (5) Ln = Pr, M = Ni, and n approximate to 33). These compounds are two-dimensional polymeric structures constructed by hydrated lanthanide cations and two types of heteropoly anions, [MV13O38](7-) and [MV12O38](12-). In contrast to the previous reported 1:13 heteropoly anions, all with disordered structures, [MV13O38] 7-clusters in 1 - 5 are non- disordered with a distinct mode. The second kind of anionic cluster [MV12O38](12-) with Oh symmetry, which consists of 13 entire edge-sharing MO6 (M = V, Mn or Ni) octahedra, has not been reported hitherto. The emergence of the new cluster may be correlated to the six capping lanthanide cations surrounding it with a stabilization effect. In this paper, the syntheses and structures of the five polymeric lanthanide heteropolyvanadates of manganese(IV) and nickel(IV) have been presented.