The Studies On The Structures And Properties Of The Functionalized Coordination Compounds Constructed By Polypyridyl, Polycarboxylate

The self-assembly of hybrid metal-organic coordination polymers have attracted much attention, due to their novel structures and potential applications in many fields. In this paper, six reported polypyridyl ligands of l,10-phenanthroline-5,6-dione (pdo), 4,5-diazafluorene-9-one (dafo), 2,2'-bipyridine-3,3'-dicarboxylate (H2bp3dc), 2,2'-bipyridine-3,3'-dicarbomethoxy (bp3dm), 2,2'-bipyridine-3,3'-diformylhydrazide (bp3dh), 4,5-diazafluorene-9-one isonicotinoylhydrazone (dfih), and one new aroylhydrazone ligands of 4,5-diazafluorene-9-one quinaldinoylhydrazone (dfqh) have been successfully synthesized. By the assembling of the above ligands or other polypyridyl and polycarboxylate based ligands with metal salts, four series of supramolecular complexes have been obtained at room temperature or under hydrothermal conditions. Furthermore, we investigated the fluorescence properties, magnetic and thermal properties of the complexes.Firstly, eight novel supramolecular complexes (I1-I8) have been synthesized by treatments of the synthesized polypyridyl ligands with different metal ions. I 1 exhibits two-dimensional network structure formed by hydrogen bonds and Ï€-Ï€ interactions;I 2 contains 1D infinite polymeric chains that are formed through nitrate bridging water molecular;Ï€-Ï€ stacking effects in I 4 extend the structure into two-dimensional network;I 3 and I5 are aroylhydrazones coordinated complexes. The hydrogen bonds and Ï€-Ï€ interactions play an important role in crystal packing and the stability of these complexes;I 6 shows a 1D linear chain structure, in which extensive hydrogen bondings between the deprotonated carboxylates, nitrate ions, and coordinated water molecules result in a 3D network which also contains face-to-face Ï€-Ï€ interactions between adjacent bp3dc ligands;I 7 is a 1D helical chain, and the interchain H-bonding interactions also contribute to the final 3D network.Secondly, the reaction of metal ions, heterocyclic diimine (2,2'-bipyridine, 1,10-phenanthroline, 2,2'-bipyridylamine) and bidentate or monodentate coeffect ligands (CN, N(CN)₂^-, Cl^-) afford nine polypyridyl complexes II1- II9. Complexes II1-113 are 1D cyanide bridged helical chains. They have different helicoids of pseudo-square, pseudo-trigonal and head-to-head bistrigonal for II1, II2 and II3, respectively. The structure of II1 is extended to 2D hexagonal meshed layers by the hydrogen bonding between terminal cyanides and lattice water molecules, which also contain Ï€-Ï€ interactions between adjacent sheets. Cu¹ ions in II1 are distorted trigonal planar coordinated by two bridging cyanides and one terminal cyanide, whereas that in II2 and II3 are pseudo-tetrahedral coordinated by two bridging cyanides and two N atoms of a diimine. Although II4- II7 exhibit the same or differentnetwork topology and dimensionality, these systems have the same chemical moiety formula. 118 involves a CunN4Cl chromophores with a regular square based pyramidal stereochemistry, while 119 involves a regular trigonal bipyramidal one. Both of the two compounds were constituted through hydrogen bonding and n-n interactions between heterocyclic rings. It should be noted that complex II1 is the first cyanide bridged Fen-Cu' complex of helical chain structure and II8 is the first example of CunN4X(X = Cl", Br", I") complexes generated from mixed ligands.Thirdly, six metal-organic polymers are synthesized by the reacting of flexible aliphatic dicarboxylates and rigid bidentate linear ligands with metal salts. IHl is a 3D network being composed of layers of octahedrally coordinated Cd atoms bridged by malonate anions in syn-anti configurations within the layers and pyrazine molecules between layers;Each Cd atom in EH2 displays uncommon pentagonal-bipyramidal geometry to form 2D infinite grid sheets with square grid dimensions of ca. 7.936 x 7.936 A;Both HI3 and IH4 exhibit ID linear -M-bipy-M-bipy- (bipy = 4,4'-bipyridine) chain polymers, and these chains were packed as ???ABCABC-- layered structures;HI5 contains the paddle-wheel cage dicopper(II) units, forming a 1D double-stranded chain structure along the a axis;IH6 is built up from two types of polymeric chains with [EuC^^O^^ units as tethers, resulting in microporous framework. The magnetic behaviors show that in IH5 the occurrence of a strong antiferromagnetic coupling between the copper(II) ions can be obtained. To our knowledge, Compound DI2 represents the first example of flexible self-assembled succinate-pyrazine mixed bridging ligand coordination network.Finally, five novel hybrid metal-organic complexes (IV1-IV5) based on aromatic polycarboxylic acid (benzene-1,3,5-tricarboxylic acid and 2,6-pyridinedicarboxylic acid) have been produced. The luminescent properties of the complexes are influenced by hydrogen bonding and coeffect ligands. Hydrogen bonding can enhance the intension of fluorescence, while the coordinated water may weaken it.