Synthesis,Structures And Photocatalytic Properties Of Supramolecular Compound Based On Polyvalent Organic Cations Template

In the past few decades, organic- inorganic hybrid crystal materials, especially supramolecular compound, have been paid extensive close attention, not only for their rich topological structures, but also because of their potential applications in a number of areas, for example host-guest recognition, catalysis and so on. In this thesis, we synthesized a series of divalent, trivalent organic cations as template agent under the condition of room temperature and self-assembly with metal halide/pseudohalide and we got 10 novel organic-inorganic hybrid supramolecules via slow evaporation approach. These compounds were characterized by IR spectrum, TG, UV-Vis spectrum, element analysis etc. In addition, we calculated their optical band gap and explored their photocatalytic properties.Firstly, we synthetized three bivalent cations, 1,2-bis[(4-aminopyridinium)-N-methylene] benzene dibromide(O-AP·2Br), 1,3-bis[(4-aminopyridinium)-N-methylene] benzene dibromide(M-AP·2Br), 1,4-bis[(4-aminopyridinium)-N-methylene] benzene dibromide(P-AP·2Br) respectively, that as structural direction reagents carriers on self-assembly with Ag/Cu halide/pseudohalide and obtained compounds 1-6, {[O-AP][Ag(SCN)3]}n(1), {[M-AP][Ag2Br3(SCN)]}n(2), {[M-AP][Cu Br3]}n(3), {[M-AP]2[Cu4I8]}n(4), {[M-AP]2[Ag4I8]}n(5) and {[P-AP]0.5[Cu(SCN)2]}n(6). Structure analysis shows that complex 1 and 3 are mononuclear; complex 2, 4 and 5 are multinuclear cubane and complex 6 is infinite two-dimensional structures. These compounds were characterized by IR spectrum, TG, UV-Vis spectrum, element analysis etc. In addition, we calculated compound 1-6 optical band gap and speculated that they could be photocatalyst. So we explored their photocatalytic properties under the condition of simulator sun-light in degradation methylene blue, methyl orange and rhdamine B dye. The results show that compound 1-6 exhibit high efficiency in degradation methylene blue dye; only compound 3 and 4 exhibit general efficiency in degradation methyl orange dye; compound 1-6 all not exhibit efficiency in degradation rhdamine B dye under simulator sun-light.Secondly, we synthetized three trivalent cations, 1,3,5-tri[(isoquinoline)-N-methylene] benzene tribromide(Tbiq·3Br), 1,3,5-tri[(isoquinoline)-N-methylene]-2,4,6-trimethyl benzene tribromide(Tbmiq·3Br), 1,3,5-tri[(quinoline)-N-methylene]-2,4,6-trimethyl benzene tribromide(Tbmqu·3Br) respectively, that as structural direction reagents carriers on self-assembly with Ag/Cu halide/pseudohalide and obtained compounds 7-10, {[Tbiq][Cu(SCN)4]}n(7), {[Tbmiq][Cu2(SCN)4N3]}n(8), {[Tbiq]2[Cu Br7]}n(9) and {[Tbmqu]2[Ag2.5Br6.5(SCN)2]}n(10). Structure analysis shows that complex 7-10 are all mononuclear or multinuclear metal cluster structure. We characterized complex 7-10 by IR spectrum, TG, UV-Vis spectrum, element analysis etc. And we analyzed the fluorescence spectrum of two trivalent cations template and complex 7-10. The results show that organic template Tbiq·3Br and Tbmqu·3Br have fluorescence, but complex 7-10 have not exhibit fluorescence. So we speculated that the introducing of metal ion make organic template come about fluorescence quenching. In addition, we calculated compound 7-10 optical band gap and speculated that they could be photocatalyst. And also we explored their photocatalytic properties under the condition of simulator sun-light in degradation methylene blue dye. The results show that compound 7-10 all not exhibit efficiency in degradation methylene blue dye. So it is also a major challenge that to desige and synthesis the high efficiency photocatalyst which could work under the condition of sun-light.