| Chapter 1 deals with the background and scope of the work. Chapter 2 describes the design, synthesis, and characterization of novel zeolitic metal oxide based materials. These materials are constructed from the vanadium oxide clusters {lcub}V18O42(X){rcub} (X = VO43− , SO42−, Cl−, Br−, OH−) that are acting as secondary building units. These clusters have cage-like structures constructed from the fusion of 18{lcub}VO5) square pyramidal units. The terminal oxo groups present as (V=O) are capable of coordinating with metal centers and their coordination complexes.; Thus, a judicious choice of the constituent building units, and reaction pH enabled us to synthesize new one-dimensional chain and three-dimensional framework materials which are represented by [LaIII2(H 2O)12VIV10VV 8O42(SO4)].30H2O and [H6Mn 3(H2O)12VIV15V V3(VVO4)].30H2O, respectively. The one-dimensional chain consists of {lcub}V18O42(SO 4){rcub} clusters linked by {lcub}La(H2O)6{rcub}3+ ions. The three-dimensional solids consist of arrays of {lcub}V18O 42(XO4){rcub}, (X = V, S) clusters inter-linked by bridging {lcub}M II(H2O)4{rcub}2+ ions (M = Mn, Fe, Co, Ni, Zn, Cd, Ca, and Mg). This arrangement generates cavities in the structures, which are occupied by cations and removable lattice water.; In an effort to see if the waters in the {lcub}M(H2O)4{rcub} linkers in these solids could be replaced by neutral ligands such as simple amines, we succeeded in preparing M2(en)5[{lcub}M(en) 2{rcub}3V18O42(X).12H2O] (M = Zn, Cd; X = CI−, Br−, or OH −). These solids are composed of {lcub}V18O42(X){rcub} clusters interconnected in three-dimensions by {lcub}M(en)2{rcub} bridges.; Chapter 3 describes the synthesis and characterization of new inorganic-organic hybrid materials composed of vanadium oxide chains or layers and metal organoamine coordination complexes. These include the three related networks [Co(en) 3V3O9].H2O, [Co(H2O)(2,2 ′-bipy)V2O6], [CO2(H2 O)2(PY)2V4O12], and four related framework materials; [Co(pz)(V2O5)2], [Co(pz)V2O6], [Co(4,4′-bipy)V 2O6], [H2Co2(4,4′-bipy) 3V4O14].2H2O. The structure of these series of compounds—the prototypical solid, [Co2(H2 O)2(PY)2V4O12], consists of vanadium oxide chain composed of corner sharing {lcub}VO4{rcub} tetrahedra. The vanadium oxide chains are cross-linked by {lcub}L-M-L′{rcub} (M = Co; L = pyridine; L′ = H2O) coordination complexes.; A change in the organoamine ligands results in structural changes in the final products. Thus, we succeeded in making [Co(pz)(V2O 5)2], [Co(pz)V2O6], [Co(4,4 ′-bipy)V2O6], and [H2Co 2(4,4′-bipy)3V4 |
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