Synthesis And Properties Of Coordination Polymers Based On Rigid Tetra-carboxylic Acids Ligands

Coordination polymers with highly ordered and infinite networks are constructed by metal ions or metal clusters and organic linkers through coordination bonds,which have promising applications in gas adsorption,catalysis,fluorescence and sensor for their novel structural features and multiple functions.This thesis mainly studies on the crystal structures and properties of coordination polymers based on two rigid tetra-carboxylic acids ligands.In Chapter 1,we give a brief review about current research and development of coordination polymers which are based on the rigid carboxylic acids ligands,and then we explicate the research proposal and significance of this thesis.In Chapter 2,we synthesized six new coordination polymers using Mn???,Co???,Cu???,Zn???,Cd???,Zr???and tetrakis?4-carboxyphenyl?siliane by solvothermal reactions:[Mn₂?TCS??H₂O?2]n?1?,[Co₂?TCS??H₂O?2]n?2?,[Cu₂?TCS??H₂O?2]n?3?,[Zr604?OH?₄?TCS?2?DMF?₄?HCOO?₄]n?4?,{[Zn3?TCS?2]·4DMF}n?5?,[Cd2?TCS?-?H₂O?2]n?6?.The compounds were characterized by X-ray single crystal diffraction,powder X-ray diffraction,FT-IR,TGA etc.Compound 3 is built based on the typical paddle-wheel[Cu₂?OCO?₄]secondary building unit?SBU?which is connected with 8 others adjacent SBUs through 4 carboxylic acids ligands,its pore width is up to nanoscale.4 is constructed based on a Zr₆O₄ cluster which is connected with adjacent clusters through the ligands TCS4-.4 has a big absorptive capacity of 408 cm3 g-1 for N₂ at 77 K,BET specific surface area is 1433.62 m2 g-1 and average pore width is 1.27 nm.Its adsorption amount of CO2 at 195 K is 378.6 cm3 g-1?16.9 mmol/g,74.8 wt%?,means that every building block could adsorb 17.5 CO2 molecules.In Chapter 3,we synthesized two new coordination polymers using Mn?II?5 Cd?II?and porphyrin ligand,5,10,15,20-tetrakis?4-carboxyphenyl?porphyrin?H₂TCPP?,by solvothermal reactions:[Mn₂?TCPP??H₂O?]n?7?,[Cd₄?TCPP?2?H₂O?2]n?8?.The compounds were characterized by X-ray single crystal diffraction,powder X-ray diffraction,FT-IR,TGA etc,and the gas adsorption and pesticide adsorption of these compounds were checked.7 is constructed based on paddle-wheel[Mn₂?OCO?₄]secondary building unit which is connected with porphyrin carboxylic acids ligands.Its adsorption amount of CO2 at 195 K is 122.3cm3 g-1?5.46 mmol/g,24.17 wt%?,means that every building block could adsorb 5 CO2 molecules.8 has an absorptive capacity of 110 cm3 g-1 for CO2 at 195 K.The adsorption experiments of six different pesticides including carbofuran,methomyl,pirimicarb,bisphenol A,2,4-dichlorophenol,triclosan demonstrate that the compound 8 has a good adsorption effect of 2,4-dichlorophenol and bisphenol A;especially for bisphenol A,the adsorption effect is up to 96.2%,the adsorption effect of 2,4-dichlorophenol is up to 91.3%.