The. [r <sub> 1 </ Sub> R <sub> 2 </ Sub> Im] <sub> A </ Sub> [pb <sub> M </ Sub> X <sub> N </ Sub>] (x = Br And I) Perovskite Inorganic - Organic Hybrid Materials, Ion Synthesis, Structure And P

In this thesis, eleven novel inorganic-organic hybrid perovskite crystal materials are synthesized under ionothermal conditions and characterized: {[EMIM]PbBr3}n (1) {[EMIM]PbI3}n(7) {[PMIM]PbBr3}n (2) {[PMIM]2[Pb2I6]}n(8) {[ALMIM]PbBr3}n (3) {[VMIM]PbI3}n(9) {[BMIM]PbBr3}n (4) {[EVIM]3[Pb3I9]}n(10) {[AMIM]PbBr3}n (5) {[PVIM]3[Pb3I8]}n(11) {[HMIM]PbBr3}n (6)The ion liquids utilized in the synthsis are 1-ethyl-3-methylimidazolium bromide ([EMIM]Br), 1-propyl-3-methylimidazolium bromide ([PMIM]Br), 1-butyl-3-methylimidazolium bromide ([BMIM]Br), 1-allyl-3-methylimidazolium bromide ([ALMIM]Br), 1-amyl-3-methylimidazole bromide ([AMIM]Br), 1-hexyl-3-methylimidazolium bromide ([HMIM]Br), 1-ethyl-3-methylimidazolium iodide ([EMIM]I), 1-propyl-3-methylimidazolium iodide ([PMIM]I), 1-ethyl-3-vinylimidazole iodide ([EVIM]I), 1-propyl-3-vinylimidazole iodide ([PVIM]I) and 1-vinyl-3-methylimidazolium iodide ([VMIM]I), which serve as solvents, templates and charge balance species.X-ray single-crystal diffraction showes that the compositions of compounds 1-6 are [R1R2IM]a[PbmBrn]. Compounds 1 and 4 belong to the orthorhombic P212121 space group.2,3,5 and 6 are in monoclinic P21/n space group. The compositions of compounds 7-11 are [R1R2IM]a[PbnIn]. Compounds 7 and 9 both belong to the orthorhombic Pbca space group.8 crystallizes in monoclinic P21/n pace group. Compound 10 is in trigonal P-3 space group, and 11 is of tetragonal 14(1)/acd space group.In compounds 1-10, the Pb centers are linked by the Br or I atoms to form 1D inorganic chains, which are connected by imidazolium cations via C-H…X weak hydrogen bonds to give the 3D supramolecular frameworks. In compound 11, the Pb atoms are firstly linked by I bridging to generate a [Pb4I4] cubane building block, which links each other to give a 3D inorganic framework with dia toplology. It should be pointed out that this Pb-I framework possesses one-dimensional channels along a- or b- axis directions (about 13.28×4.29 A2 along the a-axis direction; about 4.30×7.19 A2 along the a-axis direction), which are fully occupied by the imidazolium cations. Furthermore, compounds 1-11 have been characterized via elemental analysis, TG, FT-IR, X-ray powder diffraction, and fluorescence spectra. Solid-state UV-Vis spectra show that these compounds all are potential semiconductor materials. Moreover, the solid state CD spectrum and SHG effects are also carried out for the two compounds crystallized in the non-centric space group.