Summary: Hydrophobically substituted diallylamines bearing a hexyl, dodecyl, or octadecyl chain were synthesized and homopolymerized as hydrochlorides. Copolymerization of the diallylamines with maleic acid produces alternating copolymers. The copolymers behave as amphiphilic polyampholytes and dissolve best in the acidic or in the basic form. Only the copolymer with the hexyl chain could be dissolved in aqueous solvents and shows hydrophobic association. The copolymers with the longer alkyl chains require polar protic organic solvents. All polymers are amorphous, but show a superstructure in bulk due to their amphiphilicity. magnified image

The amphiphilic poly(ampholyte) poly(N,N-diallyl-N-hexylamine-alt-maleic acid), bearing simultaneously carboxylic acids, amines and hydrocarbon side chains, was used as a matrix to stabilize inorganic ion species (anionic as well as cationic) generated in aqueous solution from Ni(NO3)(2).6H(2)O, Co(NO3)(2).6H(2)O and (NH4)2MoO(4). Drying produces hybrid organic-inorganic blends which, due to the amphiphilicity of the copolymer, exhibit supramolecular organization in the bulk. Solid state studies show that up to two moles of metal cations (alone or together with metal anions) per repeat unit of the copolymer can be blended without loss of homogeneity in the hybrid material. A systematic screening permitted the determination of the optimal conditions for the preparation of homogeneous blends. Thermal treatment of the hybrid materials produces simple and mixed nickel and/or cobalt molybdates. The alpha- as well as the P-phase were obtained, and the mixed structures are solid solutions of simple NiMoO4 and CoMoO4

A new precursor route for the preparation of bulk oxides and thin films of bismuth vanadates is proposed. The method involves the thermal treatment under air and mild conditions of hybrid organic-inorganic precursors, made from a zwitterionic salt-free polymer matrix and selected inorganic species. Monoclinic BiVO 4 was obtained in the form of bulk oxide by calcination of the powdered homogeneous hybrid materials at 600 °C, from precursors containing Bi and V in stoichiometric amounts. In the same way, thermodiffractometry studies performed on a hybrid material exhibiting a Bi/V molar ratio of 2 revealed that the ionic conductor γ-Bi 4 V 2 O 11 phase can be stabilized under very soft thermal conditions (300 °C). Additionally, thin films of yellow monoclinic BiVO 4 were for the first time fabricated, by thermal treatment of the same hybrid polymeric precursors deposited on quartz substrates by spin coating, using a layerby-layer technique. The presence of the target phase at the surface of the plates was confirmed by X-ray diffraction as well as UV-vis measurements.