Self-assembly Chemistry Based On 1,2,4-Triazole Heterocyclic Ring, Schiff-base And Acyclic Polyether-bridged Ligands

The chemistry of organic-inorganic coordination polymers and supramolecular complexes has recently become an active area of increasing interest internationally. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. Recently, remarkable progress has been made in the area of molecular inorganic-organic hybrid polymers. The synthesis and characterization of infinite one-, two-, and three-dimensional networks have been an area of rapid growth. In this thesis, a series of ligands bridged, respectively, by 1, 2, 4-Triazole heterocyclic ring , fulvene, Schiff-base containing ethynyl, and the acyclic polyether-bridged ligands were synthesized. The coordination chemistry based on these new ligands and metal ions was investigated. A large number of new coordination compounds were prepared and fully characterized by IR, elemental analysis, X-ray single-crystal diffraction and TGA, the luminescent properties and thermal stability were investigated.I. A series of tripodal-type ligands bridged by 1, 2, 4-Triazole heterocyclic ring were synthesized, which contain–CN as terminal groups or Schiff-base with chelated configuration. One coordination supramolecule generated from the tripodal-type ligand with–CN terminal groups and Ag(I) has been synthesized. The results demonstrated that the extending directions of arms of ligands influenced the structures of resulted compounds significantly.II. The Schiff-base ligands with chelated configuration and ethynyl were designed and synthesized. Six coordination supramolecules were generated from self-assembly of these ligands and Ag(I). We found the difference in the type of silver salt influenced the configuration of coordination supramolecules when they reacted with the same ligand.III. A series of acyclic polyether-bridged ligands with–CN as terminal groups were synthesized. The self-assembly reaction of thses ligands and Ag(I) were investigated and many coordination supramolecules with large ring or cavity were obtained. The difference in substitute positions in benzene ring greatly influenced the configuration of coordination supramolecules. Some ligands coordinated to Ag(I) not only by the–CN but also by the oxygen atoms of the polyaether chains.IV. A series of flexible acyclic polyether-bridged ligands with–COOH as the terminal groups were synthesized. A lot of coordination driven and hydrogen-bond driven supramolecules were obtained by hydrothermal reactions of these ligands with d-block metals. Aslo, we added the 4,4'-bipyridine to the mixture to obtain many kinds of new coordination supramolecules. It indicated the diversity of the non-covalent interaction of the acyclic polyether-bridged ligands with–COOH as the terminal groups.V. New type of fulvene ligands were designed and synthesized. The coordination chemistry of this type of fulvene ligands with Ag(I) was investigated. A novel organic–inorganic complexe was obtained based on Ag-N and Ag-C interaction. The self-assembly chemistry based on asymmetry fulvene ligands with–CN and thiophene as coordinated groups was investigated.This study demonstrated that the use of ligands based on 1, 2, 4-Triazole heterocyclic ring , fulvene, Schiff-base containing ethynyl, and the acyclic polyether-bridged ligands as precursors to bind metal, is in fact a new and efficient approach for synthesis of novel supramolecular systems with interesting fluorescent chemical and physical properties. Also, these new coordination supramolecules may have cavity and provide the opportunity for the host-guest chemistry...