ABSTRACT
Eleven first row transition metal fluoride sulfates synthesised in hydrofluorothermal conditions have been structurally characterised by single crystal X-ray diffraction and exhibit a wide variety of structural motifs. The polyionic structures containing Ti, V, Mn and Fe vary from discrete polyhedral units in Na4TiF4(SO4)2 and [N2C10H12] TiF4SO4, through one dimensional chains in (K2FeF3SO4, Li3FeF2(SO4)2·H2O, Li1.87Ti1.13O0.39F1.61(SO4)2, [N2C10H12]TiF2(SO4)2, [N2C6H16]Fe(SO4)2F and [N2C6H16]V(SO4)2F), and to two dimensional layers in ([N2C6H16](2+)Mn2F2(SO4)2, Na2VF3SO4 and Na3CrF2(SO4)2).
ABSTRACT
The structural chemistry of hybrid organic-inorganic lead iodide materials has become of increasing significance for energy applications since the discovery and development of perovskite solar cells based on methylammonium lead iodide. Seven new hybrid lead iodide compounds have been synthesized and structurally characterized using single-crystal X-ray diffraction. The lead iodide units in materials templated with bipyridyl, 1,2-bis(4-pyridyl)ethane, 1,2-di(4-pyridyl)ethylene and imidazole adopt one-dimensional chain structures, while crystallization from solutions containing piperazinium cations generates a salt containing isolated [PbI6](4-) octahedral anions. Templating with 4-chlorobenzylammonium lead iodide adopts the well known two-dimensional layered perovskite structure with vertex shared sheets of composition [PbI4](2-) separated by double layers of organic cations. The relationships between the various structures determined, their compositions, stability and hydrogen bonding between the protonated amine and the iodide ions of the PbI6 octahedra are described.
ABSTRACT
Six new phases in the gallium-fluoride-arsenate system have been synthesised hydrofluorothermally using a fluoride-rich medium and "HAsF6" (HF : AsF5) as a reactant. RbGaF3(H2AsO4), KGaF(H2AsO4) and [piperazine-H2]2[Ga2F8(HAsO4)]·H2O have one dimensional structures, [DABCO-H2]2[Ga4F7O2H(AsO4)2]·4H2O consists of two dimensionally connected polyhedral layers, while GaF(AsO3[OH,F])2 and (NH4)3Ga4F9(AsO4)2 both have three-dimensionally connected polyhedral frameworks.
