【作者】 李敏；

【导师】 郎建平； 李宝龙；

【作者基本信息】 苏州大学 ， 无机化学， 2014， 博士

【摘要】 由金属离子和有机配体架构的配位聚合物因其迷人的拓扑结构和在荧光、催化、吸附以及非线性光学等方面具有广阔的应用前景而备受关注。近年来，含氮杂环和多元羧酸混合配体与金属离子自组装成为构筑配位聚合物的有效方法。本论文选用不同双三唑柔性配体作为主要建筑单元与过渡金属离子组装合成了一系列结构新颖的配位聚合物，并且根据这些化合物的结构特点，我们分别研究了相应化合物的催化、荧光和热稳定性等性质。主要结果简述如下：一、利用tmtz和不同的金属盐以及多元有机羧酸合成了11个配位聚合物：{[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)。受金属离子、有机配体、pH值、反应温度以及有机羧酸骨架上取代基不同等多种因素影响，配合物1-11展现出了结构多样的特点。1是一维的梯状结构。2和6结构相似，均是5-连接的二维网络。3是(4,6)-连接的三维网络。4是一维管状链。5是复杂的(3,4,4)-连接的三维网络结构。7具有手性正交晶系空间群P212121，固体CD测试证明7中存在对映体。8和9结构相似，均为比较少见的多聚穿套结构。10是(3,4)-连接的二维网络结构。11是一维阳离子链。上述化合物中，8、9和10在催化降解有机染料甲基橙的测试过程中表现出了较强的催化活性，是潜在的固体催化剂。另外锰(II)/锌(II)配位聚合物都展现了较好的荧光性能。二、利用长柔性配体btb与金属盐和多元羧酸设计合成了8个结构各异的配位聚合物：{[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)。12是由两种一维链形成的三维氢键网络。13具有(3,4)-连接的三维结构。14则是(3,5)-连接的三维网络。15是二维网格，而16具有三维结构。17是基于[Cu4(OH)2]簇的二维网络。18是由六核铜簇和单个铜组成的复杂三维结构。19是一个二重穿插的三维网络。经催化性能测试，在紫外光照射下，铜(II)配位聚合物14-18对有机染料甲基橙和罗丹明B均表现出了一定的光催化降解活性，但催化能力各不相同。三、由同样构型多变的长柔性配体bth与五种有机羧酸构筑了一系列配位聚合物：[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)。其中铜配位聚合物21和22均为二维(4,4)网络结构，而20是个复杂的二维结构。21和22经紫外光照射对甲基橙和罗丹明B表现出了一定的催化降解活性，而20没有。23-25以及28有相似的二维网格结构。具有三维和二维结构的锌配位聚合物26和27展现出较好的荧光性能。更多还原

【Abstract】 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.更多还原