Organic Functionalization Of Metal Halides And Their Structure Sensibility And Photoelectric Conversion Behavior

Recently, photoelectric functional materials based on sensitive structures have attracted great interests for their potential applications in the molecular switches, information storage and so on. The structural sensitive materials based on functionized metal halide&organics have received special attention for their high sensitivity in phase transformation. In this field, study about functional modification by the way of hybridizing photoelectric organic molecules with metal halides is still in its infancy, and chromatic, photoelectric conversion mechanism are still unclear. Therefore, the study about the synthesis and structure characterization of photoelectric functional materials based on metal halide will be significant for the development of new photoelectric functional materials.In view of the good photosensitivity of viologen molecules, we here introduced viologen molecules into metal halide system. Kept the molecular engineering theory in mind, we chose viologen&viologen derivatives (MV2+, N-PP+, BPV2+, DMP+) as the organic functional modifier, to hybridize with metal halides containing Cu+, Zn2+, Cd2+, Bi3+, in addition, we also used I2O5 as a source of the IO3-, Ln3+ as the metal ion source to synthesize iodic acid/rare earth complexes. Finally, we obtained 8 organic/metal halide hybrids and 4 iodic acid/rare earth complexes successfully by the way of solvothermal method and evaporation method: N-pp+=l-propy1-[4,4’-bipyridin]-1-ium);MV2+=methylviologen;BPV2+=(E)-1,1’-(ethene-1,2-diy1)b is(pyridin-1-ium) chloride);DMP+= (E)-4-(4-(diethy-lamino)styry1)-1-methyl-pyridin-1-ium); 4,4’-dpdo=4,4’-bipyridine-dioxide.According to structural analysis, the inorganic metal halides of compound 1-7 are zero-dimensional clusters, and the secondary bonding interactions between organic molecules and inorganic metal halides contribute to dimensional extention. Compound 1 and 2 are isomers, and their stabilities are disclosed by theoretical calculation. While in compound 9-12, the structural extention were achived by bridged IO3-, I2O62- dimer and secondary bonding interactions. Compounds 9 and 10 were 3D structures based on bridged 103- and I2O62- dimer, but compound 10 exhibited an unusual [103(μ2-O)IO2]2- asymmetric structure. Compound 11 and 12 were isomers with one-dimensional chain structure and two-dimensional layer. Compound 1,2,3,7,8 exhibit excellent reversible thermochromic and photochromic properties, among which compound 1 is more sensitive with color-change temperature of 80℃. And the thermochromatic temperatures of 2,3,7,8 are 100-150℃, specially, compound 7 is sensitive to ultraviolet light. This work will be beneficial for the development of novel structural sensitive materials.