【作者】 丁建刚；

【导师】 李宝龙；

【作者基本信息】 苏州大学 ， 无机化学， 2014， 博士

【摘要】 配位聚合物作为新型的功能性材料已逐渐成为材料化学领域的研究热点。本论文选用刚柔适中且长度恰当的含苯环的柔性三氮唑配体bbtz及mbbtz作为主配体，与多元羧酸根阴离子及过渡金属离子自组装，得到了32个具有多种结构的配位聚合物，并研究了其热稳定性和荧光性质。主要结果和结论如下：1．分别利用配体组合bbtz和sip、bbtz和1,4-ndc、bbtz和5-NO2-1,3-bdc，采取不同的合成方法得到了7个配位聚合物。1展示了一个(44·64·82)2(6)拓扑网络的2重互穿结构；2呈现一个(42·63·8)2(6)拓扑网络的二维结构；3是具有(83)2(8)拓扑网络的二维结构；4形成二维(6,3)网络，3和4均展示了2D→3D的多聚穿套结构；5形成存在自穿插的5-连接的三维网络。6形成一个(4,5)-连接的三维柱层状网络；7形成三重穿插的4-连接的65·8-CdSO4型三维网络。以上配合物的结构各不相同，说明配位聚合物的结构可以通过合成方法加以调控。化合物1-5展现了较好的荧光性能。{[Cd3(bbtz)4(sip)2(H2O)4]·12H2O}n(1){[Cd3(bbtz)3(sip)2(H2O)6]·4H2O}n(2){[Cd3(bbtz)2(sip)2(H2O)8]·4H2O}n(3){[Cd(bbtz)1.5(1,4-ndc)]·3H2O}n(4){[Cd(bbtz)1.5(1,4-ndc)]·1.5H2O}n(5)[Mn(bbtz)0.5(5-NO2-1,3-bdc)(H2O)]n(6)[Mn(bbtz)(5-NO2-1,3-bdc)(H2O)]n(7)2．利用柔性配体bbtz和苯三甲酸异构体及苯二甲酸异构体，合成了7个Cd(II)配位聚合物。8形成(42·63·72·83)2(6·72)2(7)拓扑网络的三维结构；9形成一个不寻常的(3,4,5)-连接的三维柱层状网络；10呈现一个(412·63)2(45·63·82)2(46)拓扑网络的三维结构。11展示了一个(63)(65·8)拓扑网络的三维结构；12是具有(63)2(6)拓扑网络的二维结构；13形成二维(4,4)网络；14形成一个(3,4)-连接的二维网络。以上配合物的结构各不相同，说明多元苯基羧酸异构体在配位聚合物的组装中起关键作用。化合物8-14均展现了较好的荧光性能。{[Cd3(bbtz)5(1,3,5-btc)2(H2O)2]·2.5H2O}n(8){[Cd3(bbtz)4(1,2,4-btc)2(H2O)2]·7H2O}n(9){[Cd3(bbtz)(1,2,3-btc)2]·H2O· CH3OH0.75}n(10)[Cd(bbtz)0.5(1,2-bdc)(H2O)]n(11)[Cd3(bbtz)4(1,2-bdc)2Cl2]n(12){[Cd(bbtz)(1,3-bdc)(H2O)]·H2O}n(13){[Cd(bbtz)0.5(1,4-bdc)(H2O)]·CH3OH}n(14)3．利用bbtz及mbbtz与均苯四甲酸合成了四个配位聚合物。15是具有(63)(64·82)(67·83)拓扑网络的三维结构；16形成(4,4)-连接的三维柱层状网络；17是一维链结构；18形成(3,4)-连接的的三维柱层状网络。15和16的结构并不相同，说明双三氮唑甲基-苯异构体在配位聚合物的组装中起关键作用。{[Zn2(bbtz)2(btec)(H2O)]·4H2O}n(15){[Zn2(mbbtz)2(btec)]·2H2O}n(16){[Co(mbbtz)(btec)0.5(H2O)3]·2H2O}n(17){[Cd2(bbtz)(btec)(H2O)4]·4H2O}n(18)4．利用bbtz和4,4’-二苯醚二甲酸及丁烯二酸合成了9个配位聚合物。19形成二重多聚互锁的二维(4,4)网络，20是铁轨型结构，21形成(3,4,6)-连接的三维柱层状网络，22、23形成三重穿插的三维金刚石网络，24形成二维(4,4)网络，25、26、27都形成平面状二维(4,4)网络，(4,4)网络层相互穿插形成三维结构。19、20和21结构差异巨大，说明了金属离子对配位聚合物组装的显著影响；而25、26和27是同构的，又说明了金属离子对配位聚合物组装的调控作用的大小，也取决于含氧羧酸配体提供的环境。22、23和24是体现金属离子调控作用适中的例子。化合物19、20、22、23与25均展现了较好的荧光性能。{[Cd(bbtz)(oba)(H2O)]·H2O·(DMF)2}n(19)[Zn(bbtz)1.5(oba)]n(20){[Mn(bbtz)(oba)(H2O)]·0.5H2O}n(21){[Cd(bbtz)(mal)(H2O)]·H2O}n(22)[Zn(bbtz)(mal)]n(23){[Co(bbtz)(mal)(H2O)]·H2O}n(24)[Zn(bbtz)(fum)(H2O)2]n(25)[Co(bbtz)(fum)(H2O)2]n(26)[Mn(bbtz)(fum)(H2O)2]n(27)5．利用bbtz与1,4-苯二甲酸、1,3-苯二甲酸及1,3-苯二乙酸合成了5个配位聚合物。28和31都形成二维(4,4)网络，但28中的二维网络存在二重多聚互锁；29形成(4,6)-连接的三维柱层状网络；30展示了一个(4·64·85)2(42·63·8)(8)拓扑网络的三维结构；32形成二维砖墙式网络。其中28和29都是采用缓慢扩散法制备的，但模板阴离子不同，这导致了其最终产物的结构差异巨大，说明了模板阴离子有时会对结构产生重要的影响。31和32的结构差异体现了苯基多元羧酸由刚性到柔性的变化对配合物结构所产生的影响。{Co(bbtz)(1,4-bdc)(H2O)2]·2H2O}n(28)[Co3(bbtz)4(1,4-bdc)3(H2O)4]n(29){[Mn(bbtz)(1,4-bdc)(H2O)]}n(30)[Co(bbtz)(1,3-bdc)(H2O)]n(31)[Co(bbtz)(1,3-pda)(H2O)]n(32)更多还原

【Abstract】 As the new functional materials, coordination polymers have been gradually turnedinto the hotspot on the research of materials chemistry. In this thesis,1,4-bis-((1,2,4-triazol-1-yl)methyl)benzene (bbtz) and1,3-bis((1,2,4-triazol-1-yl)methyl)-benzene(mbbtz) which possess medium length and flexibility were chosen as the primary ligandsto react with the auxiliary polycarboxylates and transition metal ions, and thirty-twocoordination polymers were synthesized. The thermal stabilities and fluorescent propertieshave been investigated. The results and conclusions were briefly described as follows:1. Seven coordination polymers were synthesized by the slow diffusion, directreaction and hydrothermal methods using1,4-bis((1,2,4-triazol-1-yl)methyl)benzene (bbtz)and sulfoisophthalate (sip),1,4-naphthalenedicarboxylic acid,5-nitroisophthalic acid.1shows a novel two-fold interpenetrating3D network with (44·64·82)2(6) topology.2displays an unusual2D network with (42·63·8)2(6) topology.3exhibits an unusual2Dnetwork with (83)2(8) topology and a2D3D polythreaded network.4exhibits a2D (6,3)network and a2D3D polythreaded network.5reveals a self-catenated3-connected3Dnetwork.6shows a (4,5)-connected3D pillar-layer network.7exhibits a4-connected65·8-CdSO43D network. The diverse structures demonstrate that the structures ofcoordination polymers can be tuned by the synthesis methods.1-5exhibit good fluorescentproperties.{[Cd3(bbtz)4(sip)2(H2O)4]·12H2O}n(1){[Cd3(bbtz)3(sip)2(H2O)6]·4H2O}n(2){[Cd3(bbtz)2(sip)2(H2O)8]·4H2O}n(3){[Cd(bbtz)1.5(1,4-ndc)]·3H2O}n(4){[Cd(bbtz)1.5(1,4-ndc)]·1.5H2O}n(5)[Mn(bbtz)0.5(5-NO2-1,3-bdc)(H2O)]n(6)[Mn(bbtz)(5-NO2-1,3-bdc)(H2O)]n(7) benzenedicarboxylate isomers were synthesized.8shows a3D pillar-layer network with(42·63·72·83)2(6·72)2(7) topology.9reveals a unusual (3,4,5)-connected3D pillar-layernetwork.10displays a3D network with (412·63)2(45·63·82)2(46) topology.11shows a3Dnetwork with (63)(65·8) topology.12exhibits a2D network with (63)2(6) topology.13exhibits a2D (4,4) network and a3D hydrogen bonding architecture.14consists of a(3,4)-connected2D network and a3D hydrogen bonding architecture. The diversestructures demonstrate that the benzenetricarboxylate and benzenedicarboxylate isomersplay the key role in the assembly of the coordination polymers. All these complexesexhibit good fluorescent properties.{[Cd3(bbtz)5(1,3,5-btc)2(H2O)2]·2.5H2O}n(8){[Cd3(bbtz)4(1,2,4-btc)2(H2O)2]·7H2O}n(9){[Cd3(bbtz)(1,2,3-btc)2]·H2O·CH3OH0.75}n(10)[Cd(bbtz)0.5(1,2-bdc)(H2O)]n(11)[Cd3(bbtz)4(1,2-bdc)2Cl2]n(12){[Cd(bbtz)(1,3-bdc)(H2O)]·H2O}n(13){[Cd(bbtz)0.5(1,4-bdc)(H2O)]·CH3OH}n(14)3. Four coordination polymers were synthesized using bbtz and benzenetricarboxylate,benzenedicarboxylate isomers.15reveals a3D pillar-layer network with (63)(64·82)(67·83)topology.16displays a (4,4)-connected3D pillar-layer network.17shows1D chainstructure.18exhibits a (3,4)-connected3D pillar-layer network. The diverse structures of15and16indicate that the isomers of polydentate azoly ligands play the key role in theassembly of the coordination polymers.{[Zn2(bbtz)2(btec)(H2O)]·4H2O}n(15){[Zn2(mbbtz)2(btec)]·2H2O}n(16){[Co(mbbtz)(btec)0.5(H2O)3]·2H2O}n(17){[Cd2(bbtz)(btec)(H2O)4]·4H2O}n(18)4. The combination of bbtz ligand and auxiliary polycarboxylic acids(4,4’-Oxybisbenzoic acid, maleic acid, fumaric acid) provided nine coordination polymers.19shows a polycatenated2D (4,4) network.20displays a railroad structure.21reveals a(3,4,6)-connected3D pillar-layer network.22,23display a two-fold interpenetrating3Ddiamondiod network.24exhibits a2D (4,4) network.25,26,27are isostructural and exhibit the interpenetrating2D planar (4,4) network. The distinct structures of19,20and21indicate that metal ions play the key roles in the structures of coordination polymers.Otherwise,25,26,27are isostructural and it implies that the tuning function of metal ionlies on the circumstance of polycarboxylate.22,23and24are the example of displayingthe medium tuning function of metal ion on the structures of coordination polymers.19、20、22、23and25exhibit fine fluorescent properties.{[Cd(bbtz)(oba)(H2O)]·H2O·(DMF)2}n(19)[Zn(bbtz)1.5(oba)]n(20){[Mn(bbtz)(oba)(H2O)]·0.5H2O}n(21){[Cd(bbtz)(mal)(H2O)]·H2O}n(22)[Zn(bbtz)(mal)]n(23){[Co(bbtz)(mal)(H2O)]·H2O}n(24)[Zn(bbtz)(fum)(H2O)2]n(25)[Co(bbtz)(fum)(H2O)2]n(26)[Mn(bbtz)(fum)(H2O)2]n(27)5. The mixed ligands of bbtz and auxiliary polycarboxylic acids(1,4-benzenedicarboxylic acid,1,3-benzenedicarboxylic acid,1,3-phenylenediacetic acid)afforded five coordination polymers.28exhibits a polycatenated2D (4,4) network.29reveals a (4,6)-connected3D pillar-layer network.30displays a3D network with(4·64·85)2(42·63·8)(8) topology.31shows a2D (4,4) network.32shows a2D brick wallnetwork.28and29were synthesized by the slow diffusion method with different anionictemplates, their distinct structures indicate that anionic templates sometimes play animportant roles in the structures of coordination polymers. The diverse structures of31and32imply the influence of the transform from rigidity to flexibility of the aromaticpolycarboxylate on the assembly of the coordination polymers.{Co(bbtz)(1,4-bdc)(H2O)2]·2H2O}n(28)[Co3(bbtz)4(1,4-bdc)3(H2O)4]n(29){[Mn(bbtz)(1,4-bdc)(H2O)]}n(30)[Co(bbtz)(1,3-bdc)(H2O)]n(31)[Co(bbtz)(1,3-pda)(H2O)]n(32)更多还原