Synthesis, Structures And Properties Of Coordination Compounds Based On Polyoxometalate And In Situ Reaction

The design and construction of novel metal-organic coordination polymers have attracted increasing attention currently owing to their widespread applications in many fields such as catalysis, magnetism, photoelectricity, material, gas storage, as well as their fascinating architectures and topologies. Many acidification learning as an emerging interdisciplinary subject is gradually developing and play a more significant role, especially in the development of catalyst aspects. Generally, coordination polymers are composited by reactions of pre-synthesized or commercially available ligands and metal ions. As an effective synthetic route, in situ generating novel ligands under hydro-or solvothermal conditions, then incorporates the final structures has attracted considerable attention for new organic synthesis and unexpected coordination complexes. In this paper,9 novel metal-organic coordination compounds based on polyoxometalate and in situ reaction have been constructed and measured by single-crystal X-ray crystallography, powder X-ray diffraction, thermal analysis, catalysis, electrochemical properties, luminescence and elemental analysis. The text is divided into five chapters, each chapter is as follows:In the preamble of the first chapter, the basic principles and concepts of coordination chemistry and metal organic chemistry have been briefly presented. We focus on the synthesized methods of coordination compounds, polyoxometalate types and affected factors, kinds of in situ ligand reactions.In chapter two, a pair of anion-induced isomers {Co4(dimb)4(H20)g[K(H20)H6P5W30O110]}n-122H20 (1) {Co4(dimb)4(H20)g[K(H20)H6P5W30O110]}n-90H20 (2)were synthesized and characterized based on Preyssler P5W30. In the chapter, we introduced in detail the induced effect of the anions and electrocatalytic abilities.In chapter three, four members of Preyssler P5W30-based inorganic-organic hybrids{[Cu12(pbtz)2(Hpbtz)2(OH)4(H20)16][Na(H20)P5W30O110]}-16H20 (3), {[Cu10(ttbz)2(Httbz)4(OH)6(H20)8][K(H20)H2P5W30O110]}-30H20 (4), {[Ni6(bpz)6(H20)16][Na(H20)H2P5W30O110]}-36H2O (5), {[Co4(bpz)6(H20)9][K(H20)H6P5W30O110]}46H20 (6) were constructed under hydrothermal conditions and determined by different methods.In chapter four, we achieved the controlled in situ ligand reaction by employment of different steric hindrance between maleic acid and fumaric acid and obtained two metal-organic coordination polymers{[Cu4(trz)2(mal)2(H2O)2]-3H2O}n (7), {[Cu5(trz)2(mal)2(fma)(H2O)4]-2H2O}n(8).In chapter five, A two-dimensional Ag(I) coordination polymer [Ag(Htzsuc)]n (9) generated through unusual in situ aza-Michael addition reaction of 1H-1,2,4-triazole and fumaric acid during hydrothermal treatment. Moreover, the thermal stability and luminescent property of 9 were discussed.