The Design, Synthesis, Structure And Characterization Of Coordination Polymers Based On The 2-iodine-4-sulfobenzoic Acid

In this thesis, we use a new ligand 2-iodine-4-sulfobenzoic acid (H2isba) to react with transition metal ions in the presence of N-containing auxiliary ligand (bix, bbtz, bimb, phen,2,2’-bipy, etc.), leading to the formation of eighteen coordination polymers by adopting the typical solution method and hydrothermal method. The influence of metal ions, the auxiliary ligand, reaction temperature and solvent on the crystalline architectures of coordination polymers have been discussed. All the complexes were characterized by IR spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. The structure-property relationship is further investigated.The work of this paper consists of the following three parts:1. Eight coordination polymers were obtained based on the 2-iodine-4-sulfobenzoic acid (H2isba), the transition metal ions [Ni(Ⅱ), Co(Ⅱ), Mn(Ⅱ)] and N-containing auxiliary ligands. Complexes{[Ni(isba)(bix)2(H2O)]·H2O}n(1) and {[Ni(isba)(bbtz)2(H2O)]·H2O}n (2) are obtained under hydrothermal condition and exhibit two-dimensional (2D) structure, which further extend into 3D supramolecular network through hydrogen bonding. Complex{[Ni(isba)(4-bpum)]·2H2O}n (3) crystallizes in the monoclinic system with space group P2(1)/n. H2isba adopts chelating coordination mode. The Ni(II) ions are linked by both H2isba and 4-bpum in this complex. An extended 3D structure was formed by C-H...I hydrogen bonding. The reaction of Co(II) with H2isba in the presence of the auxiliarly ligand bix yielded two new coordination polymers:[Co(isba)(bix)2(H2O)]·H2O}n(4), which crystallizes in the orthorhombic system with the space group Pbca, and{[Co(isba)(bix)]}n (5) which crystallizes in the monoclinic system with, the space group P21. Complex {[Co(isba)(bbtz)2(H2O)]·H2O}n(6) crystallize in the same space group as 4. Complex {[Co(isba)(4-bpum)]·2H2O}n (7) and complex 3 have the same space group. Complex {[Mn(isba)(bix)2(H2O)]·H2O}n (8) forms a 2D layer structure and extends into a 3D supramolecular network through hydrogen bonding. Complexes 2 and 6 show reverible uptake to water molecules.2. Five Cu(II) coordination polymers were obtained based on the 2-iodine-4-sulfobenzoic acid in the presence of N-containing auxiliary ligands. The asymmetric unit of complex{[Cu2(isba)2(bix)2(H2O)]·H2O}n (9) consists of two crystallographical independent Cu(II) ions, the Cu(1) ion is four-coordinated, while the Cu(2) ion is five-coordinated. Complex{[Cu(isba)(bbtz)2(H2O)]·H2O}n (10) exhibits a distorted octahedral coordination geometry and forms a 2D layer structure. Complex [Cu(isba)(btb)1.5]·3H2O}n (11) crystallizes in the triclinic system with the space group P-1, which exhibits a 3D pillared-layer network architecture. Complex {[Cu(isba)(phen)(H2O)]}n (12) and Complex {[Cu(isba)(2,2-bipy)(H2O)]}n(13) form a double-chain structure, further extending into a 3D supramolecular network through hydrogen bonding. Interestingly, complexes 11 and 12 exhibit reversible desorption-adsorption behavior to water.3. Five coordination polymers were obtained based on the 2-iodine-4-sulfobenzoic acid, the transition metal ions [Zn(II), Cd(II), Pb(II)] and N-containing auxiliary ligands. Complex {[Zn(isba)(bix)(H2O)]}n (14) are prepared under solvalthermal condition. Complex{[Zn(isba)(bbtz)2(H2O)]·H2O}n(15) can be gained using two different synthetic methods. The asymmetric unit of complex {[Cd(isba)2(bimb)2(H2O)]·3H2O}n (16) consists of two Cd(II) ions, which both exhibit a slightly distorted octahedral coordination geometry. Complex {[Cd(isba)(4-bbpum)0.5(H20)2]·3H2O}n(17) crystallizes in the triclinic system with space group P-1. The Cd(II) ions are linked by both isba2- and N-containing auxiliary ligand, further extending into a 3D supramolecular network through hydrogen bonding. Complex{[Pb(isba)(phen)]·H2O}n (18) exhibits a 2D layer structure. The weak interactions (π-π stacking and hydrogen bonding) further extend the 2D layer into 3D supramolecular architecture. Complexes 15,16 and 18 exhibit relatively strong fluorescent emission.