Incorporation of Ions into Giant Molybdenum-oxide Cluster as a General Phenomenon


In spite of the integration and concomitant release of all 16 {Mo1} (necessary for ions Recently, the integration of different kinds of matter into giant wheel-shaped molybdenum-oxide clusters has been investigated with so-called chemical adaptability phenomenon. This refers to the integration of a large number of appropriate cations and anions even of the large “salt like” {M(SO4)}16 rings (M = K+ or NH4+) based on the cooperative/synergetic activation of silent receptor sites. An even more remarkable consequence of the flexibility behavior of the molecular giant wheel-shaped molybdenum-oxides of the type {Mo176} and {Mo154}: the possibility of the integration of Cu2+ as tetrahedrally coordinated divalent cations at the same wheel area. In this study and in order to make the phenomenon as a general, the incorporation of ions into giant molybdenum-oxide cluster was expanded to involve the integration of some other cations (Fe2+, Co2+, Ni2+ or Zn2+) or salt like ring{Tl(SO4)}16. Uptake and almost half of the 16 {Mo2} units the parent ring structure is maintained in the following resulting hybrids {(Mo146) (K(SO4))16} 1compound, {(Mo146) (NH4(SO4))16} 2 compound and {(Mo146) (Tl(SO4))16} 3. Moreover, the integrating of a tetrahedrally coordinated divalent cation like Fe2+, Co2+, Ni2+ or Zn2+ in addition to Cu2+, at the same wheel area (after releasing six {Mo2}-type building blocks of the parent wheel-shaped cluster) produced hybrid compounds with the general formula: [H4MIIn MoV28MoVI114O432(H2O)58]-26+2(n-5) (where MII= Fe2+, Co2+, Ni2+ or Cu2+, n=5, but with Zn2+, n=6) compounds (4–8). The result corresponds to the extreme flexibility of molybdenum-oxide building block linking resulting in the formation of a huge variety of structures from “molybdate” containing solutions (a unique molybdenum-oxide diversity phenomenon). The prepared compounds were characterized by CHN, Cit.Tit for the determination of the number of the MoV centers, spectroscopic methods (IR and UV-Vis) and X-ray crystallography (determination of the characteristic unit cell dimensions).