Build A New Type Of Metal - Organic Coordination Polymer Structure, Characterization And Properties Of Organic Carboxylic Acid Ligands

The aim of this thesis is the synthesis of new metal-organic coordination polymers on the basis of organic multi-carboxylate ligands, which are "decorated" or "bridged" by various organic N-donor ligands. The study on synthetic conditions and rules for these hybrid compounds for these compounds are also carried out.Seven new metal-organic coordination polymers and two novel metal-oxo clusters compounds have been synthesized on the basis of hydrothermal technique and/or organic solvent synthesis methods and structurally characterized by elemental analyses, IR, EPR, XPS, TG, 51V NMR and single crystal X-ray diffractions. The thermal stabilities, fluorescent properties of these compounds have been studied.1. Three new metal-organic coordination polymers have been hydrothermally synthesized by the introduction of 1,2,4-H3btc and 1,2,4,5-H4btc and structurally characterized:{[Co(H2O)2][Co2(phen)2(btc)2]}n (1){[Fe(phen)(btc)(OH2)]2·CH3CH2OH}n (2)[Cu2(2,2'-bipy)2(btec)]n (3)Compounds (1)³ exhibit different structural characteristics. It is found that the use of carboxylate ligands and different latter transition metals may influence the self-assembly of the compounds. Compound (1) exhibits a novel two-dimensional network with unusual (4,6)-lattice-type network, and H3btc ligands connect the metal centers to form one dimer. Compound (2) possess a novel metal-organic supramolecular framework constructed by 1,2,4-H3btc. Compound (3) represents a new infinite 1-D ladderlike chain architecture constructed from btec ligands.2. One new latter transition metal-oxalate hybrid compounds have been synthesized in the hydrothermal condition by virtue of oxalate building blocks. The crystal structures have been characterized:[Zn3(C2O4)3(4,4'-bipy)4]2n (4)Compound (4) exhibits a novel two-dimensional network which consists of infinite zinc (II) oxalate chains connected to each other by bridging and terminal ligand 4,4'-bipy ligands alternately.3. Three new metal-organic coordination polymers have been hydrothermally synthesized on the basis of adipate ligands and the introduction of different N-donors. The crystal structures have been characterized: [Co(OOC(CH2)4COO)(4,4'-bipy)] (5){Cd[O2C(CH2)4CO2][1,10'-phen]}n (6){Cd2(C2O4)[O2C(CH2)4CO2(OH2)2][2,2'-bipy]}?H2O (7)Compound (5) exhibits a novel three-dimensional interpenetrating network. Compound (6) possesses a novel one-dimensional chain, and represents the first dinuclear compound connected by the mixed adipate and 1,10'-phen ligands. Compound (7) exhibits an interesting 3-D network and represents the first example in which both 2,2'-bipy and oxalate group are introduced into the {M/adipate} system. Furthermore, the introduction of oxalate ligand has led to the dimensional transformation of the metal-adipate coordination polymers.These observations indicate that compounds (6) and (7) maybe excellent candidates for photoluminescence materials.4. Two new metal-oxo clusters compounds have been hydrothermally synthesized and structurally characterized:(H3O)3[AsMo12O40(VO)6]·6H2O (8)(NH4)4[H12VV12O36(VIVO4)]·11H2O (9)Compound (8) is the first hexacapped Keggin-type molybdovandoarsenate. Compound (9) is the first Keggin-type polyvanadate.