Synthesis And Characterization Of The Perovskite-type Organic-Inorganic Hybrids And Their Doped Compounds

The layered perovskite-type organic-inorganic hybrids integrate performace advantagesof both organic and inorganic on a molecular level, have inspired great interests for scientificstudy due to their unique electronic, optical and magnetic properties. Doping is an importantmeans in the modified materials and preparation of new materials. The layeredperovskite-type compounds which have special structures and properties are prepared withdoping.Three hybrids based on n-butylamine and three hybrids based on ethylenediamine wereprepared by liquid phase synthesis, and metal ions doping was also studied. The structuresand properties of the synthetic products were characterized by using elemental analysis, IR,X-ray diffraction, thermogravimetric and differential scanning calorimetric analyzer.The hybrids of [NH₃（CH₂）₂NH₃]MCl₄（M=Cu, Mn, Cd）,（C₄H₉NH₃）₂MCl₄（M=Cu, Mn,Cd）. The perovskite-type hybrids analysis shows that the structures of products are typicallayer, which are consistent with the expectation. The groups of organic amine between theinorganic layers exist with protonated form of NH₃⁺, and combine with inorganic layers inN-H…Cl hydrogen bonding. The hybrids have a good thermal stability with thedecomposition temperature higher than200℃. The hybrids have2³obvious endothermicpeaks of solid-solid phase transtions, a lower phase transition temperature and a higherenthalpy of solid-solid phase transtions under200℃.The doped compounds were synthetized such as （C₄H₉NH₃）₂Cu_0.90Mn_0.10Cl₄,（C₄H₉NH₃）₂Cd_0.75Cu_0.25Cl₄,（C₄H₉NH₃）₂Cd_0.60Mn_0.40Cl₄,[H₃N（CH₂）₂NH₃]Cu_0.90Mn_0.10Cl₄,[H₃N（CH₂）₂NH₃]Cd_0.70Cu_0.30Cl₄,[H₃N（CH₂）₂NH₃]Cd_0.75Mn_0.25Cl₄.The doping has no effecton the structures of the compounds with layer structure. The doping has little effect on the thermal stability of the hybrids, the doped compounds have a good thermal stability with thedecomposition temperature higher than200℃. The doping has a certain influence onsolid-solid structure phase transition of the hybrids. Compared with the parent compounds,transformation enthalpy of （C₄H₉NH₃）₂Cd_0.75Cu_0.25Cl₄,（C₄H₉NH₃）₂Cd_0.60Mn_0.40Cl₄,[H3N-（CH₂）₂NH₃]Cd_0.70Cu_0.30Cl₄are significantly reduced, while [H₃N（CH₂）₂NH₃]Cd_0.75Mn_0.25Cl₄is significantly increased.