Syntheses,Crystal Structures And Properties Of Compounds Based On Semi-rigidity And Rigidity N-containing Ligands And A Heterothiometallates Metal Cluster

We have chosen one rigid V-shaped ligand(L1, BPFP =2,8-di（pyridin-4-yl）dibenzofuran and one semi-rigid ligand（L2, BBMB =4,4’-bis（（1H-benzo[d]imidazol-1-yl）methyl）-1,1’-biphenyl） to design and synthesis seven novel coordination polymers using hydrothermal methods. In addition, we have synthesis one cluster coordination polymer using monomeric W/S/Cu clusters as building blocks and the rigid linear bi-imidazole ligand（L3, BIMB = 1,4-di（1H-imidazol-1-yl）benzene） as linkers. These compounds have been characterized by elemental analysis, IR, X-ray single-crystal diffraction methods. Meanwhile, the Power X-ray diffraction（PXRD）analyses and thermogravimetric analyses were carried out to confirm the phase purity and the thermal stabilities of the compounds. In addition, the solid-state UV-vis absorption spectra were also investigated. This thesis covers three parts as follow:1. Five novel Co（II） coordination polymers have been synthesized using rigid V-shaped ligand BPFP with four different auxiliary carboxylic ligands, namely[Co（BPFP）2（bpda）]n（1）-（2）, [Co（BPFP）2（sca）]n（3）, [Co（BPFP）2（sda）]n（4） and[Co2（BPFP）4（oba）2·H2O]n（5）, where H2 bpda = 1,1’-biphenyl]-4,4’-dicarboxylic acid, H2sca= succinic acid, H2 sda = thiophene-2,5-dicarboxylic acid, 4,4’-H2 oba = 4,4’-oxydibenzoic acid. Compounds 1 and 2 were obtained through one-pot reaction and are framework-isomeric. Compound 1 generates a 1D infinite chain structure while compound2 is a 3-fold interpenetration framework with honeycomb-like nets. Compounds 3 and 4 are isostructural except that the sca2–anions in 3 are replaced by the sda2–anions in 4 and the sca2–anions and sda2–anions bridge the adjacent 1D chain as pillars to form a 2D sheet.Furthermore, the same 2D sheets interpenetrating each other generate a 2D→2D polyrotaxane networks. Compound 5 shows a 2D sheet structure with an 8-member ring with {Co2C2O4} and BPFP ligands coordinate with Co（II） atoms as mono-denatate ligand.2. Two another novel Co（II） coordination polymers have been synthesized using one semi-rigid ligand BBMB and two auxiliary carboxylic ligands, namely[Co（BBMB）1.5（oba）]n（6）, and [Co（BBMB）（m-bdc）]n（7）, where 4,4’-H2 oba =4,4’-oxydibenzoic acid, m-H2 bdc = 1,3-benzenedicarboxylate. Compound 6 shows a stable1 D chain due to the presence of π···π interactions. Compound 7 generates a 2D sheet structure by bi–dentate BBMB ligands and μ1,1-m-bdc2–anions bridge the Co（II） ions without any weak interactions. By changing auxiliary carboxylic ligands, we obtained two sets of compounds（3 and 4, 6 and 7）. While 3 and 4 are isostructural, 6 and 7 are different.The possible reason may be the different rigidity between BPFP and BBMB.3. One cluster coordination polymer has been obtained using monomeric W/S/Cu clusters as building blocks and the rigid linear bi-imidazole ligand BIMB as linkers.[WS₃Cu₃OBr（BIMB）_2.5·H₂O]_n（8）In cluster 8, the central W atom is seven coordinated by three μ3-S atoms and three Cu（I）atoms and a terminal oxygen atom to form a nest-like [WS3Cu3O] Secondary building unit（SBU）. The adjacent nest-like [WS3Cu3O] SBUs are linked by cis–configuration BIMB ligands forming a 1D chain. Furthermore, the adjacent 1D chains are linked by trans–configuration BIMB ligands to form a 2D→2D double-sheet framework.