Synthesis, Crystal Structures And Properties Of Coordination Polymers With Flexible Bis(1,2,4-triazol-1-ylmethyl)Benzene Ligands

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)...