Syntheses, Structures And Functions Of Coordination Polymers Involving 5,10,15,20-tetrapyridyl Porphyrin/Copper/Phosphorus

Coordination polymers is one class of coordination compounds with repeating coordination entities extending in 1,2,or 3 dimensions,which have a extensive application potential in the field of luminescent,magnetic,semiconductive materials and microporous materials.Metalloporphyrinic coordination polymer（MCP）is the coordination polymer using porphyrin or metalloporphyrin as linkers and metal ions or metal cluster as nodes.Copper（I）/phosphorous compounds,consisting of Cu（I）,phosphorous ligand and other auxiliary ligands,have a potential applications as luminescent materials owing to its various structures and excellent luminescence.Morever,they also can be used as nodes to construct coordination polymers.Considering the photochromic feature of azobipyridine and the excellent catalytic properties of metalloporphyrin,we aimed to construct coordination polymers using metal-5,10,15,20-tetrapyridylporphyrin（M-TPyP,M=Mn,Ni,Sn）and azobipyridine as linkers and Cu（I）/phosphorous as nodes,then explore their structures,functions and applications.In this thesis,we used azobis（4-pyridine）as linkers to assemble with [Cu（PPh₃）₂X]（X = Cl,Br,I）and obtained three coordination polymers with the structure of 1D infinite zigzag chain,[（PPh₃）₂Cu₂（μ2-Cl）₂(μ-azobis（4-pyridine）（CH₂Cl₂）]n（1）,[（PPh₃）₂-Cu₂（μ2-Br）₂(μ-azobis（4-pyridine）]n（2）and [（PPh₃）₂Cu₂（μ2-I）₂(μ-azobis（4-pyridine）]n（3）,they all show an sharp intense red luminescence about 700nm;Using hexamolybdates and octamolybdates as anion templates,self-assembly of azobis（4-pyridine）/azobis（3-pyridine）with Cu（CH₃CN）₄ClO₄ yield two zigzag chain-like caiton coordination polymers [Cu₂（CH₃CN）₄（azobis（4-pyridine））₂]W6O19（4）and [Cu₄（CH₃CN）₈（azobis（3-pyridine））₄]Mo₈O₂₆·2CH₃CN₅).We functionalised covalently hexamolybdates using m-（methylthio）aniline and p-（methylthio）aniline to produce two mono-substituted organoimido derivatives of hexamolybdate,（Bu₄N）₂[Mo₆O₁₈（NC₆H₄-SCH₃-p）]（6）and（Bu₄N）₂[Mo₆O₁₈（NC₆H₄SCH₃-m）]（7）,which are characterized by single crystal X-ray diffraction,FT-IR spectra,UV-vis spectra,elemental analysis,1H NMR and cyclic voltammetry.Assembly of TPyP with copper/phosphorous compouds via solution diffusion resulted in a perchlorate of [Cu（TPyP）],{H₃[Cu（TPyP）]}（ClO₄）₃（8）;The solventhermal reaction of MnCl₂ and TPyP give a double layer of 2D network [MnCl（MnCl₂TPyP）]n（9）.Assembly of [Sn（OH）₂（TPyP）] and [Cu（PPh₃）₂（CH₃CN）₂]-ClO₄ afforded a 2D network {Cu₂[(P（C₆H₅）₃]₄[Sn（OH）₂TPyP]（ClO4）₂}n（10）.Assembly of [Ni（TPyP）]/[Mn（TPyP）] and [Cu（PPh₃）₂（CH₃CN）₂]ClO₄ afforded two 3D framework Cu[(P（C₆H₅）₃][Ni TPyP]_0.75ClO₄（11）and Cu₄[(P（C₆H₅）₃]₄[MnCl₂TPyP]₃（12）with pore size of 12.6?.Compound 8-12 are characterized by IR,single crystal X-ray diffraction,powder X-ray diffraction and TGA.The catalytic activity of compound 12 on the epoxidation of alkenes was investigated,and the influence of different solvents and oxidation regants,amount of oxidation regant,amount of catalyst,reaction temperature and reaction time on this reaction was systematically investigated.We found that iodosobenzene as oxidation regent in 1.5 mole equivalents,5% e.q catalyst and acetonitrile as solvent to react at room temperature for 4h,the yield of styrene oxide run up to 95.7% with the selectivity of 91.4%.