Syntheses, Characterization Of Transitional Metal-Organic Complexes Based On Rigid Polycarboxylic Acid

In recent years, the design and synthesis metal-organic polymers has attracted considerable attention in the academia, owing to their potential applications in gas adsorption and separation, catalysis, photochemical sensors, molecular magnetism, and so on. Hydrothermal reactions of Co(Ⅱ)/Mn(Ⅱ)/Ni(Ⅱ)/Cd(Ⅱ)/Cu(Ⅱ) salts and 1,1’:4’,1":4",1’"-quterphenyl-2,4,2’",4’"-tetracarboxylic acid (H4qptc) in the presence of corresponding auxiliary N-donor ligands [4,4’-bibp=4,4’-bis(imidazolyl)biphenyl,1,4-bib= 1,4-bis(1-imidazoly)benzene,4,4’-bimbp=4,4’-bis(imidazol-1-ylmethyl)biphenyl,1,3-dpp= 1,3-di(4-pyridyl)propane and phen=1.10-phenanthroline] resulted in eleven novel complexes, formulated as following: {[Mn2(qptc)(4,4’-bibp)(H2O)4]·2H2O}n(1) [Mn2(qptc)(1,4-bib)(H2O)8]n (2) [Co2(qptc)(4,4’-bimbp)(H2O)2]n(3) {[Mn2(qptc)(1,4-bib)(H2O)2]·2H2O}n(4) [Ni2(qptc)(1,4-bib)(H2O)8]n (5) [Co2(qptc)(1,3-dpp)(H2O)3]H2O}n(6) [Cu3(qptc)1.5(bipy)7(H2O)]n(7) [Cu(qptc)0.5(2,2-bipy)(H2O)]n(8) [Co(qptc)0.5(2,2-bipy)(H2O)]n(9) [Cd2(qptc)(phen)2]n(10) {[Ni(qptc)o.5(H20)2]·2H2O}n (11)The single-crystal X-ray diffraction analysis shows that polymer 1 is a 4,6-connected porous 3D framework with the point symbol (44.62)(44.610.8), which is composed of infinite 2D networks pillared by 4,4’-bibp bridging ligand. Polymer 2 is a 1D zigzag chain, and the adjacent chains are extended to a 3D supramolecular by non-covalent interactions involving contributions from carboxyl-water clusters. Polymer 3 is a 2D layer framework with an unprecedented topology, which are packed into a 3D supramolecular architecture by π…π and C-H…π interactions. Polymer 4 consists of infinite 2D networks pillared by 1,4-bib bridging ligand giving a 4,6-connected porous 3D framework with the point symbol of (44.610.8)(44.62). Polymer 5 possesses a 1D zigzag chain structure, and the adjacent chains are further connected into a 3D supramolecular by non-covalent interactions involving contributions from carboxyl-water clusters. Polymer 6 is a 4,6-connected 3D network with the Schlafli symbol of (3.4.54)(32.4.55.66.7). Polymer 7 is a 4,4-connected 2D wavy layer with the Schlafli symbol of (64.72)2(66). Polymer 8 is isomorphic with polymer 9 and is a latticed 2D layer with the Schlafli symbol of sql. Polymer 10 is a 4,4-connected binodal 3D network with the topological type of lvt. Polymer 11 is a 1D chain structure, and the adjacent chains are connected into a 3D supramolecular by intermolecular hydrogen bonds. Polymers 1-11 were further characterized by elemental analysis, IR spectroscopy, thermal analysis and X-ray power diffraction analysis. Furthermore, the magnetic susceptibility of polymers 1-6 have been investigated. Polymers 1 and 6 display the weak antiferromagnetic behavior, polymer 2 shows weak ferromagnetic interactions, and polymers 3-5 present changing magnetic property following system temperature. The fluorescent property of polymer 10 was also investigated, and a red shift has been observed.