Synthesis,Structure,Properties And Applications Of Metal-organic Supramolecular Compounds Based On 2,2':6',2"-Terpyridine-4-carboxylic Acid

Metal-organic supramolecular compounds are advanced solid-state functonal materials because of not only novel structures but also potential applications in luminescence,molecular recognition,etc.In this thesis,based on 2,2':6',2"-terpyridine-4-carboxylic acid(Htpc),or combined with fumaric acid(H2fm)or 4,4',4"-tricarboxylic acid triphenylamine(H3ntb),three series of nineteen new metal-organic supramolecular compounds are synthesized from above organic ligands and divalent or trivalent metal ions.Their structures are determined by single-crystal X-ray diffractions.The crystalline samples were characterized by elemental analysis(EA),infrared spectroscopy(IR),thermogravimetric analysis(TG),powder X-ray diffraction(XRD),etc.From 2,2':6',2"-terpyridine-4-carboxylic acid(Htpc)and the metal salt of Cr3+?Ba2+?Rh3+?Pb2+?Zn2+or Ni2+ ions,respectively,six new metal-organic supramolecular compounds are synthesized under solvothermal conditions,namely,[Cr2(tpc)2(HCOO)2(OH)2](H2O)4(1),[Ba(tpc)2(H2O)2]n(2),[Rh(Htpc)Cl3](CH3OH)(3),[Pb(Htpc)(NO3)2](CH3CN)(4),[Zn2(tpc)2(NO3)2]n(5)and {[Ni(tpc)(H2O)2](NO3)} n(6).Seven new metal-organic supramolecular compounds are synthesized under solvothermal conditions from 2,2':6',2"-terpyridine-4-carboxylic acid(Htpc)and fumaric acid(H2fm)as well as the metal salt of Ln3+(Ln=Eu3+,Ce3+,Pr3+,Nd3+),Zn2+,Mn2+or Pb2+ions,respectively.They are {[Ln(tpc)(fm)0.5(NO3)(H2O)](H2O)}n(7-10,Ln=Eu,Ce,Nd,Pr),{[Zn(tpc)(fm)0.5](H2O)}n(11),{[Mn(tpc)(fm)0.5](H2O)}n(12)and[Pb2(tpc)(fm)(NO3)(H2O)]n(13).Six new metal-organic supramolecular compounds are synthesized under solvothermal conditions from 2,2':6',2"-terpyridine-4-carboxylic acid(Htpc)and,4',4"-tricarboxylic acid triphenyl-amine(H3ntb)as well as the metal salt of Zn2+,Cd2+ or Mn2+ ions,respectively.They are {[Zn(Hntb)(Htpc)](H2O)4}n(14),[Zn5(tpc)3(ntb)(Hntb)2(H2O)2]n(15),{[Cd3(tpc)2(Hntb)2(H2O)2](H2O)}n(16),{[Cd2(tpc)2(Hntb)(H2O)](O2O)4}n(17),{[Cd(tpc)(H2ntb)](H2O)}n(18)and{[Mn2(tpc)2(Hntb)(H2O)2]}n(19).It is particularly noteworthy is that,at room temperature,the solid-state compounds 14-17 emit red fluorescence which are very rare examples in metal(?)-organic complexes.In preliminary application study,some fluorescent supramolecular compounds are used for the preparation of photosensitive combined material from polymethyl methacrylate(PMMA,organic glass).And some compounds with good fluorescence effect are utilizated to the fluorescence or ultraviolet detection of some hydrated ions.