Design, Synthesis And Properties Of Coordination Polymers Based On Carboxyphosphinate Ligands

Design and synthetize coordination polymers with complicate structures and novel properties are one of the central issues in the field of chemistry and materials science. Organic-inorganic hybrid acids are well designed ligands, which contain both organic acids and inorganic acids features. We designed and synthesized three new carboxyphosphinate ligands: 2-carboxyethyl(phenyl)phosphinic acid(H2L), 4,4’-phosphinicobis-benzoic acid(H3La) and 4,4’-phosphinicobis-1,3’-benzenedicarboxylic acid(H5Lb). We synthesize functional coordination polyers by controling reaction conditions and adding some secondary ligands contained N atoms. In this paper, we design and synthetize 20 novel coordination polyers, Determine its crystal structure, and for some of them, we measure its magnetic and fluorescent properties.In the first chapter, we introduce the research progress of organic-inorganic hybrid acid complexes and significance of this topic.In the second chapter, we design and synthetize six coordination polyers with 2-carboxyethyl(phenyl)phosphinic acid(H2L) and Cd2+、Cu2+、Mn2+、Co2+、La3+ act as coordinated metal ions. We get compound1 and 2 with noncentrosymmetric and symmetric architecture by adjustment of the reaction pH values under the same conditions. Compound 3 exhibits weak ferromagnetism. And compound 4 and 5 exist antiferromagnetic interaction. For compound3, there is a 1D chain Cu-O-Cu and the distance between Cu-Cu in this 1D chain is 4.4808(8)?. Cu(1)-O(1)-Cu(1) bond angle is 129.088(122)°, which illustrates an efficient magnetic exchange coupling. Both 4 and 5 contain 1D metal chains, In the 1D chain, the O-P-O connection between the metal complexes increase antiferromagnetic couplings.In the third chapter, it is desirable to obtain high-dimensional coordination polymers, we design and synthetize ligand 4,4’-phosphinicobis-benzoic acid(H3La) and get 11 coordination polyers with H3 La and diverse transition metals,Compound 7~11 have 1D pore. At room temperature, compound 10 has a strong fluorescence emission at 480 nm. The enhancement of luminescence in 10 may attributes to ligand-to-metal charge transfer(LMCT). While compound 10 undergoes a red-shif. For the compound 11, carboxyl group and hypophosphite oxygen atoms connect with metal ions, forming a paddle-wheel structure, Which play a significant role in structural support. Its porosity is 49.2%, and 11 has high catalytic efficiency for the reactions of hydrogen peroxide oxides diphenylcarbazide. By adding chelating ligand 1,10’- phenanthroline(1,10’-phen), we get 1D compound 12 ~ 14, While under the same conditions, compound 15 exhibits 2D structure, it attributes to the change of coordination modes. By adding secondary ligand 4-bpmp, both of the compound 16 and 17 acts in 3D networks.In the fourth chapter,we design and synthetize 3 coordination polyers with 4,4’-phosphinicobis-1,3’-benzenedicarboxylic acid(H5Lb) and Cu2+、 Co2+、 Ag+ coordinated metal ions. The most intriguing feature of the structure of 20 is the presence of ligand unsupported Ag-Ag interactions, 20 displays novel five- and six-coordination. For compound 20, it represents a blue photoluminescence with an emission maximum at ca. 493 nm upon excitation at 350 nm at room temperature. The luminescence of 20 can be attributed to the Ag(I) cluster-based centers therein. Given the oxidizing nature of the Ag(I), a appropriate assignment for the emission involves excited states derived from ligand-to-metal charge transfer(LMCT) mixed with d-s/d-p character, The shorter Ag-Ag distances at room temperatures resulte in a red shift.