Synthesis, Structures And Optical Properties Of Supramolecular Compound Based On Polyvalent Organiccations And Ligand

In this thesis, we synthesized a series of divalent, trivalent and organic cations with coordination site as template agent then introduced them to self-assemble with metal halide/pseudohalide to abtain 13 novel organic-inorganic hybrid supramolecules via slow evaporation approach. What’s more, the template effect of different cations and optical properties of these complexes were explored.Firstly, we synthesized bivalent cations 1,ω-bis(4-methylpyridine)alkane salts(ω=3-7, abbreviate into bmpp, bmpt, bmppt, bmph and bmphp) as structural direction reagents and introduced them to self-assemble with Cu SCN. Complexes 1-5 were obtained, namely {(bmpp)[Cu2Br2(SCN)2]}n(1), {(bmpt)[Cu2(SCN)4]}n(2), {(bmppt)[Cu2(SCN)4]}n(3), {(bmph)[Cu4(SCN)6]}n(4) and {(bmphp)[Cu2(SCN)4]}n(5). Structure analysis shows that compounds 1, 2, 3 and 5 are infinite two-dimensional structures while compound 4 is a novel 1D chain structure. In addition, we explore their photocatalytic properties. The results show that complexes 1-5 exhibit high efficiency in degradation methylene blue under ultraviolet light.Secondly, we employed two trivalent cations 1,3,5-tri(4’-methylpyridiniumyl-N-methylene)-2,4,6-trimethylbenzene tribromide(Tbmpm·3Br) and 1,3,5-tri(4’-methylpyridiniumyl-N-methylene) benzene tribromide(Tbpm·3Br) as structural direction reagents and self-assembled with Cu Br, Cu SCN Ag Br and Ag SCN. Complexes 6-10 were prepared, namely, {[Tbmpm][Cu3Br6](Me OH)}(6), {[Tbmpm][Cu2(SCN)5]}n(7), {[Tbmpm][Ag4Br7]}n(8), {[Tbmpm]0.5[Ag2Br2.79(SCN)0.71]}n(9) and {[Tbpm][Cu2(SCN)5]}n(10), respectively. Structure analysis shows that compound 6 is a trinuclear copper cluster, compound 7 exhibits an anion complex composed of 1D chain and mononuclear structure, compounds 8 and 9 present similar 1D silver cluster. More interesting, compound 10 possesses a rare 2D polypseudorotaxane structure.Finally, three 4,4’-bipyridinium derivative bications, namely 1,1’’-[1, 2-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide(1,2-PMBP·2Br), 1, 1’’-[1,4-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide(1,4-PMBP·2Br) and N, N’-dibenzyl-4,4’-bipyridinium dibromide(DBBP·2Br) were synthesized and assembled with Ag Br and Pb I2. We obtained complexes 11-13, {[1,2-PMBP] [Ag5Br7]}n(11),{(1,4-PMBP)[Pb4I10]?DMF}n(12) and {(DBBP)2[Pb5I8Br6]}n(13). Compound 11 is 3D coordination polymer, 12 and 13 are 1D chains possessing incomplete cubane subunit. More interesting, compound 11 has obvious photochromic phenomenon, UV-Vis spectrum and ESR show that this phenomenon may cause by cation radicals.These compounds were also characterized by IR spectrum, PXRD, elemental analysis, TG and fluorescence spectrum.