Synthesis, Structures And Properties Of Coordination Polymers Based On1,10-Phenanthroline/Imidazole Derivatives And Polycarboxvlates Mixed Ligands

In this thesis, rigid1,10-phenanthroline (1,10-phen) derivatives[dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq)] and bis(imidazole) derivatives[1,1′-(1,4-butanediyl)bis(imidazole)(biim-4) and1,4-bis(imidazol-1-ylmethyl)benzene (bix)]have been selected as the main ligands, different organic carboxylates as the auxiliary ligandsto react with different main group and transition metal ions under hydrothermal conditions.Seventeen new complexes have been obtained and characterized by elemental analyses, IR,TG and single-crystal X-ray diffraction. The electrochemical and fluorescent properties of thesome complexes have been studied.1. Six new complexes were synthesized under the hydrothermal conditions based ondipyrido[3,2-d:2′,3′-f]quinoxaline (dpq) as main ligand and four kinds of polycarboxylic acids(2-H2CMSN=2-carboxymethylsulfanyl nicotinic acid, H2ADTZ=2,5-(s-acetic acid)dimercapto-1,3,4-thiadiazole,5-SSPIA=5-sulfoisophthalic acid sodium salt and H2BDC=1,1′-biphenyl-2,2′-dicarboxylic acid) as the secondary ligands to react with different maingroup and transition metal ions. The complexes1–6show dinuclear unit (0D)–twodimensional (2D) different structural features. The effects of the central metals andpolycarboxylic acids on the structures of the title complexes have been discussed.[Ni2(dpq)2(BDC)2(H2O)5]·H2O (1)[Pb2(dpq)2((BDC)2]·H2O (2)[Pb(dpq)(CMSN)](3)[Cd(dpq)(CMSN)(H2O)](4)[Cd(dpq)(ADTZ)](5)[Cd2(μ3-OH)(dpq)2(SSPIA)]·H2O (6)Complex1possesses dinuclear unit, which is extended into3D supramoleculararchitecture by hydrogen bonding and π–π stacking interactions. Complex2is an unusual0D+1D cocrystal of Pb(II) binuclear units and left-/right-handed helical chains, which isultimately packed into a3D supramolecular structure through hydrogen bonding interactions.Complex3shows a2D network bridged by2-CMSN anions, which is finally extended into a3D supramolecular structure through π–π stacking interactions. Complex4exhibits a1D chain，which is further extended into a2D supramolecular layer through π–π stackinginteractions. Complex5displays2D (4,4) network. Complex6is a2D structure based ontetra-nuclear CdIIcluster with the topology symbols (43)2(46·66·83), which is finally extendedinto a3D supramolecular framework through π–π stacking interactions. The diverse structuresof complexes reveal that the different coordination environment and geometry of the centralmetal atoms, the carboxylates with different coordination sites and flexibility play importantroles in the construction of the title complexes.2. Eleven new complexes were synthesized under the hydrothermal conditions based onflexible1,1′-(1,4-butanediyl)bis(imidazole)(biim-4) and semi-rigid1,4-bis(imidazol-1-ylmethyl)benzene (bix) as main ligand and two kinds of S-containingdicarboxylates2-H2CMSN and H2ADTZ as the secondary ligands to react with differenttransition metal ions. The influences of the central metals and dicarboxylates on the structuresof the title coordination polymers have been investigated.[Zn(2-CMSN)(biim-4)](7)[Co2(2-CMSN)2(biim-4)(H2O)4](8)[Ni(2-CMSN)(biim-4)0.5(H2O)2](9)[Cd(2-CMSN)(biim-4)0.5(H2O)2](10)[Cd(ADTZ)(biim-4)1.5]·5H2O (11)[Ni(bix)1.5(2-CMSN)(H2O)]·2H2O (12)[Co2(bix)2(2-CMSN)2(H2O)]·H2O (13)[Cd(bix)(2-CMSN)(H2O)](14)[Zn(bix)(2-CMSN)]·2H2O (15)[Cd(bix)(ADTZ)(H2O)](16)[Zn(bix)(ADTZ)]·H2O (17)Complexes7–11are coordination polymers based on flexible biim-4ligands. Complex7shows a2D undulated sheet, which is finally packed into a3D supramolecular frameworkthrough hydrogen bonding interactions. Complexes8–10exhibit a similar2D (4,4) gridnetwork, the layers of8and10are packed through hydrogen bonding interactions to generatea2D supramolecular framework. Complex11displays a3D diamond-type architecture.Complexes12–17are coordination polymers based on semi-rigid bix ligands. Complex12features1D ladder-like double chain structures. Complexes13and14are isomorphous andexhibit the2D networks. Complex15displays a2D sheet derived from1D [Zn-L]n‘’-likechains and bimetallic Zn2(2-CMSN)2loops. Complex16shows a2D undulated network withthe Schl fli symbol of (3·52)(32·53·64·7). The3D supramolecular architecture of complexes 12–16are stabilized by hydrogen-bonding interactions. Complex17is a3D4-foldinterpenetrated dia network. The different structures of complexes suggest that differentcentral metals and dicarboxylates play important roles in the construction of resultingarchitectures.