Synthesis,Structure And Properties Of Novel Photochromic And Proton Conducting Crystals

In this dissertation,crystalline complexes with novel conductive and photochromic properties are obtained.In coordination chemistry,transition metal complexes of carboxylic acid ligands play an important role,but there are relatively few studies on proton conduction.In this dissertation,a number of transition complexes were synthesized using ethyl violin cation(EV²⁺)as the main ligand and different aromatic carboxylic acids,H₃BTC（terephthalic acid）and m-H₂BDC（m-phthalic acid）,as the auxiliary ligands.The photochromic properties of the donor-acceptor complexes were studied by UV-visible spectrum and the proton conduction of them were studied by EIS.The specific contents are as follows:1.Three complex anion-EV²⁺donor-acceptor complexes were synthesized with ethyl violin cation(EV²⁺)as the main ligand and H₃BTC as the auxiliary ligand:（EV）_0.5[Ni（BTC）（H₂O）₅]·H₂O（1）,（EV）_0.5[Co（BTC）（H₂O）₅]·H₂O（2）and{（EV）[Cd₃（m-BDC）₄]·H₂O}（3）.Three complexes were analyzed by IR spectrom and XRD.Interestingly,complexes 1,2,and 3 showed consistent photochromism when irradiated with an ultraviolet lamp.The photochromic behavior may be due to aggregation caused by ethyl viologen cations in the solid.This work provided valuable insights into the design of new photochromic materials.Conductivity test was performed on complex 3,and the highest proton conductivity reached 1.87×10^-4S/cm.2.Taking electron-deficient EV²⁺as the guest and electron-donating carboxylic acid group as the host unit,two aromatic carboxylate anion-EV²⁺donor-acceptor complexes were synthesized:[（EV）（H₃BTEC）₂]·2H₂O（4）,（EV）（H₂BTEC）]（5）.Complexes 4 and 5have three-dimensional hydrogen bonds frameworks,and all both of them were analyzed by UV-visible spectra.Complexes 4 and 5 display photochromic properties with characteristic absorption bands centered at 420 nm and 610 nm.The proton conductivity properties of complex 4 were tested and the highest proton conductivity was 7.09×10^-4S/cm.3.Using phosphomolybdic acid as ligand,compound[（H₃O）₆(Mo₇O₂₄)]·4H₂O（6）was successfully prepared by hydrothermal synthesis.Using sodium azide as the bridging ligand,a centrally symmetric tetra-nuclear Cd（II）complex[Cd₂（N₃）₄（DMF）₃]₂（7）was synthesized by slow evaporation at room temperature.Using EV²⁺and Zn Br₂as raw materials,one polyhalide anion-ethyl viologen donor-acceptor complex was synthesized:[（EV）₂（Zn Br₄）₂]（8）.In the infrared spectrum of compound 6,a characteristic peak of the polymolybdenum oxygen cluster compound appeared clearly.In the UV-vis spectrum of compound 6,a LMCT transition occurs around 207 nm,while the bridge oxygen-metal charge transfer transition is split.The proton conduction properties of complex 6 were mainly studied,and the highest proton conductivity reached 9.12×10^-5S/cm.