Synthesis, Crystal Structure And Properties Of Organic-inorganic Hybrid Perovskite Molecular Materials

With the development of science and technology, materials research are more relied on the self-assembly of molecular materials. Organic-inorganic hybrid perovskite compounds are a new kind of molecular materials, which offer an important opportunity to combine useful properties from two chemical realms, organic and inorganic compounds, within a molecular scale composite. Such materials not only possess diversified structures, but also display unique characteristics. Considerable attention have been attracted because of their interesting molecular topologies and crystal packing motifs along with potential applications in many areas including separation, catalysis, magnetism, optics as well as electrical conductivity.In the dissertation organic-inorganic hybrid materials were synthesized and characterized by elemental analysis, FT-IR spectra, UV-Vis spectra and x-ray single crystal diffraction. The structures have been further optimized through calculation software and nonlinear optical properties were also calculated to explore relationship between structures and properties within a single structure family. The main content is shown as follows:1, Synthesis and characterization of organic-inorganic hybrid materials. The organic components have been chosen are: butylamine, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminoacetophenone, 2-aminothiazole, 1,2,3-benzotriazole, 2-amino-4-methylthiazole, 1,10-phenanthroline hydrate and 4,4'-bipyridine. The inorganic components are: tin chloride, copper chloride, zinc chloride, cobaltous chloride, nickel chloride and manganese chloride. Those hybrid materials were synthesized and characterized. Fourteen crystal structures of those compounds were analyzed by x-ray single crystal diffraction. 2, Crystal structures of compounds1-14. Compound 1: (C₄H₉NH₃)2.SnCl₆. The weak intermolecular N-H...Cl hydrogen bonds assembled the butylamine and SnCl₆^2- into layer structures. The distance between inorganic mental layers is 10.756(?). Compound 2: (C₄H₉NH₃)2.CoCl₄. The structure and weak interactions is same as compound 1. The distance between inorganic mental layers is 11.665(?). Compound 3: (NH₃C₆H₄COOCH₃)2.SnCl₆. The N-H...Cl hydrogen bonds link the 3-aminobenzoic acid methyl ester and SnCl₆^2- ions into layer structures. The distance between inorganic mental layer is 12.520(?). Compound 4: (NH₃C₆H₄COOCH₃)4.SnCl₆.2Cl_. The N-H...Cl hydrogen bonds link the 4-aminobenzoic acid methyl ester and SnCl₆^2- ions into layer structures. The distance between inorganic layers is 13.975(?). Compound 5: (NH₃C₆H₄COCH₃)₂.CuCl₄. The N-H…Cl weak interactions link the 4-aminoaceto phenone and SnCl₆^2- into layer structures. The distance between inorganic mental layers is 12.531(?) Compound 6: (NH₃C₆H₄COCH₃)₂.SnCl₆. The N-H…Cl and C-H…Cl weak interactions link the 4-aminoacetophenone and SnCl₆^2- into layer structures. The inorganic layers has two layer mental ions. The distance is 7.328 and 10.160(?). Compound 7: (NH₂C₃H₂NHS)₂.SnCl₆ and (NH₃C₃H₂NS)2.SnCl₆. The former is two dimensional structure. The latter is layer structure formed through N-H…Cl and C-H…Cl weak interactions. The layer distance is 7.918(?). Compound 8: (NH₃C₃H₂NS)2.CoCl₄. The N-H…Cl and C-H…Cl weak interactions link ^2-aminothiazole and CoCl_<sub>4^<sup>2-into layer structures. The layer distance is 7.861(?). Compound 9: (NH₂C₃H₂NSCH₃)2.ZnCl₄. The N-H…Cl weak interactions link ^2-amino-4-methylthiazole and ZnCl_<sub>4^<sup>2-into one dimensional chain structure. Compound 10: (NH₂C₃H₂NSCH₃)2.CoCl₄. The N-H…Cl weak interactions link ^2-amino-4-methylthiazole and CoCl_<sub>4^<sup>2-into one dimensional chain structure. Compound 11: (C₆H₄N₃H₂)3Mn₂.50Cl₈(H₂O)4. The N-H…Cl weak interactions link 1,2,3-benzotriazole and Mn5Cl₁64- into layer structures. The layer distance is 9.815(?). Compound 12: (C₁₂H₈N₂)2Mn2Cl₄. It is chain structure of complex 1,10-phenanthroline and Mn ions. The chains are further linked into layer structure byÏ€-Ï€weak interactions. The layer distance is 10.465(?). Compound 13: (C₁₂H₈N₂)Co3(CH₃COO)6. It is complex of 1,10-phenanthroline and Co ions, bridging linked by acetate group. Compound 14: (C10H8N2H₂)2Mn2Cl₈. The hybrid compound of 4,4'-bipyridine and Mn ions chain. In the layer structures the distance is 15.902(?).3, Optimized structures of the single crystals and models. The inorganic mental structures change more than the organic molecules in the optimized structures. With regard to the inorganic metal ions, the bond length is longer. The octahedron geometry of the SnCl₆^2- is distorted. The tetrahedron geometry of CuCl₄^2-,CoCl₄^2-,ZnCl₄^2-,NiCl₄^2- distorted severely. Two bonds are close and the tetrahedron is flat. As for CuCl₄^2- and NiCl₄^2-, the tetrahedron geometry maybe turned into square planar geometry. With regard to the organic molecules, the C-H and N-H bond length is longer. The C-H bonds can be elongated and rotated for NH₃ group. While it can be elongated, rotated and turned for NH₂ group leading to the NH₂ and phenyl become nonplanar. The atomic charges change distribution after optimized. All the changes are favorable for the forming of N-H…Cl hydrogen bonds. It can be concluded that proton is preferring bonding at heterocylic N atom to NH₃ group from the molecular energy.4, Nonlinear optical properties of the organic-inorganic hybrid compounds. The optical properties of four homologous series are investigated, which are butylamine, aminobenzoic acid, aminoacetophenone and aminothiazole series. The results can be discussed in three points. The first is that the number and orientation of organic molecules is important to the nonlinear optical properties. The second is that the various substituent and different position can affect theβvalue. The third is that he various mental ions can control the change ofβvalue to a certain extent. The Cu ions affect theβvalue more than the Sn ions.