The Construction Of D¹⁰ Transition Metal Coordination Polymer And Its Luminescence Properties

During the last two decades,metal organic coordination polymers（CPs）have become the focus of research in the field of coordination chemistry,not only due to their intriguing structures and diverse topologies but also the wide range of potential applications as functional materials in photochemical areas,gas storage and separation,molecular recognition,catalysis,nonlinear optics,and biomedical imaging.Synthesis of novel CPs with expected structures and functions by tuning the influence factors in the self-assembly process is of significant importance both in theoretical study and practical applications.This thesis focuses on the design and synthesis of diverse CPs based on d¹⁰ transition metals with interesting luminescence properties.All the complexes have been synthesized and characterized by X-ray single crystal diffraction analysis,thermal analysis,elemental analysis and IR spectra.In our research,the summary of the major achievements is as follows:（1）Fabrication of novel CPs through the dual-ligand strategy.Nitrogen-containing rigid ligand 5-（pyrazinyl）tetrazole（Hptz）has been widely used in the construction of intriguing CPs with unique application aspects due to its various coordination modes as well as strong coordination ability.While the investigation of Hptz-carboxylatesystem with d¹00 transition metal ions is inconclusive and not well understood.Therefore we employed different carboxylate ligands（terephthalic acid,1,4-H₂bdc;isophthalic acid,1,3-H₂bdc;benzenetricarboxylic acid,1,3,5-H₃btc）to react with Hptz and Zn（II）/Cd（II）metal salts,and successfully obtained six structurally different metal-organic coordination polymers,namely,[Cd（Hptz）（Hbtc）（H₂O）₂·H₂O]_n（1）,[Cd₂（ptz）（btc）（H₂O）₂·2H₂O]_n（2）,[Cd₂（ptz）₂（p-bdc）]_n（3）,[Cd₂（ptz）₂（m-bdc）（H₂O）]_n（4）,[Zn₂（ptz）（btc）（H₂O）₂·H₂O]_n（5）,and[Cd₂（ptz）（btc）（DMA）（H₂O）·4.5H₂O]_n（6）.The luminescence properties of complexes1-6 have been investigated at room temperature.All of them exhibit strong blue emission under UV light irradiation.Moreover,complexes 1 and 6 show the luminescence quenching phenomenon with the presence of Cu²⁺,suggesting that the two complexes could be considered as luminescent probes for Cu²⁺.（2）Template synthesis strategy to construct interesting metal halides.The solvent Ln（III）ions were used as the template to assist the generation of Ag（I）/Cu（I）metal coordination polymers.By employing different kinds of solvents,we successfully obtained ten complexes,namely,{[Eu（H₂O）₈][Ag₈I₁₁]}_n（7）,{[Tb（H₂O）₈][Ag₈I₁₁]}_n（8）,{[Eu（DMF）₈][Ag₆I₉]}_n（9）,{[Tm（DMF）₈][Ag₆I₉]}_n（10）,{[Eu（H₂O）₈[Ag₁₅I₁₈]}_n（11）,{[Tb（H₂O）₈[Ag₁₅I₁₈]}_n（12）,{[Eu_0.531Tb_0.117Tm_0.352（DMF）₈][Ag₆I₉]}_n（13）,{[Tb（DMSO）₇（CH₃OH）][Cu₅I₇]·I}_n（14）,{[Tb（DMF）₈][Cu₈I₁₁]}_n（15）and{[Eu_0.37Tb_0.31Tm_0.32（DMF）₈][Cu₈I₁₁]}_n（16）.Their structures and luminescence properties have been studied in detail.Moreover,the metal halides 13 and 16 with doped lanthanide ions could exhibit white light emission,which provides a convenient and promising strategy to acquire unique white light-emitting materials.