Synthesis, Crystal Structures And Properties Of Coordination Polymers With Bis-triazole Ligands

The design and construction of coordination polymers by reactions of metal ions withmultitopic ligands have attracted considerable attention. This is due to their intriguingstructural topologies and their potentials for use as functional materials in fluorescence,catalysis, adsorption and nonlinear optics etc. The employment of transition metal salts withmulti-carboxylic acids and multidentate N-donor heterocyclic ligands has become aneffective approach. In this thesis， a series of new functional coordination polymers withflexible bis-triazole ligands were designed and synthesized. Their catalytic properties,luminescent properties and thermal stability were investigated. These results were brieflydescribed as follows:1. The reaction between metal salts, tmtz and polycarboxylic acids with differentsynthesis conditions such as metal ions, pH values, temperature provided elevencoordination polymers:{[Mn(tmtz)0.5(OH-bdc)(H2O)2]·3H2O}n(1),[Mn(tmtz)1.5(1,3-bdc)]n(2),[Mn(tmtz)(1,4-bdc)]n(3),[Co(tmtz)(oba)]n(4),{[Co4(tmtz)2(bptc)2(H2O)7]·3.5H2O}n(5),{[Ni(tmtz)1.5(1,3-bdc)]·0.5H2O}n(6),[Ni(tmtz)(oba)(H2O)]n(7),{[M(tmtz)(H2O)4][M2(tmtz)2(sip)2]·xH2O}n(M=Cu (8), x=4;Zn (9), x=3),{[Zn3(tmtz)2(sip)2(H2O)4]·2H2O}n(10),{[Zn(tmtz)2(H2O)2](NO3)2}n(11).1-11exhibit the diverse structures.1exhibits a1D ladder structure.2and6have similar5-connected2D networks.3has a (4,6)-connected3D network.4shows a1D tubular-likechain.5exhibits a complicated (3,4,4)-connected3D network.7displays a2D (4,4)network, which crystallizes in the chiral orthorhombic space group P212121. The solid-statecircular dichroism (CD) spectra confirmed the occurrence of the spontaneous resolution of7. The structures of complexes8and9are similar with unprecedented polythreadedframework.10exhibits a (3,4)-connected2D network.11shows a cationic chain.8,9and10shows good catalytic activity in catalytic degradation of methyl orange and arepotential solid catalyst. In addition, manganese(II) and zinc(II) coordination polymersexhibit good luminescent properties.2. Eight coordination polymers,{[Co(btb)(H2O)4][Co(btec)(H2O)4]·12H2O}n(12), {[Co2(btb)(btec)(H2O)4]·4H2O}n(13),{[Cu(btb)(OH-bdc)]·H2O}n(14),{[Cu(btb)0.5(glu)]·H2O}n(15),{[Cu(btb)(I-bdc)]·H2O}n(16),{[Cu4(OH)2(btb)(sip)2(H2O)2]·2CH3OH·5H2O}n(17),[Cu7(btb)4(sip)4(OH)2(H2O)2(CH3OH)4]·7H2O}n(18),[Mn(btb)(I-bdc)]n(19) weresynthesized by using long flexible ligand btb, metal salt and polycarboxylic acids.12shows3D hydrogen bonding network containing two kinds of1D chain.13exhibits a(3,4)-connected3D network.14is a (3,5)-connected3D network.15is a2D network.16has a3D structure.17is a2D network based on the [Cu4(OH)2] clusters.18is acomplicated3D network with the six-core copper clusters and a single copper.19reveals atwo-fold interpenetrating3D architecture. The experiments of methyl orange(MO) andrhodamine(RhB) degradation resulted that copper(II) coordination polymers14-18haddifferent photocatalytic activity under UV light irradiation.3With the long flexible ligand bth and five organic polycarboxylic acids, a series ofcoordination polymers [Cu(bth)(1,3-bda)(H2O)]n(20),[Cu(bth)(1,3-bdc)(H2O)]n(21),[Cu(bth)(fum)(H2O)2]n(22),[Co(bth)(1,4-bdc)(H2O)2]n(23a),[Co(bth)(1,4-bdc)(H2O)2]n(23b),[Co(bth)(fum)(H2O)2]n(24),{[Zn(bth)(1,3-bda)]·2H2O}n(25),[Zn2(bth)2(NO2-bdc)2]n(26),[Zn(bth)(1,4-bdc)(H2O)2]n(27),[Cd(bth)(1,4-bdc)(H2O)2]n(28) were synthesized. Copper(II) coordination polymers21-22exhibit2D networks,20isa complex2D structure.21and22show photocatalytic activity under UV light irradiation.23-25and28have the similar2D networks. Zinc(II) coordination polymer26and27showgood fluorescent properties.