Synthesis, Crystal Structure And Properties Of The Transition Metal Coordination Polymer Constructed With Carboxylic Acid Ligand

Research on transition metal coordination polymers with intriguing structural motifs andpotential application is one of the most active topics in coordination chemistry, materialschemistry and supramolecular chemistry. In particular, the chiral metal-organic coordinationpolymers are currently attracting increasing attention owing to their fascinating applications inthe enantioselective synthesis, unsymmetrical catalysis, nonlinear optical, magnetic andferroelectric properties. So it is important significance of synthesis,crystal structure andoptical property of the transition metal and aromatic carboxylic acid coordination complexes.Seven new novel coordination polymers [Co（bdc）（py）2]n（1）、[Cu（bdc）（py）2]n（2）、[Mn（bdc）（phen）]n（3）、[Cd（bdc）（phen）]n（4）、{[Co（pydc）·（H2O）2]·0.5H2O}n（5）、{[Ni（pydc）·（H2O）3]·H2O}n（6）、[Zn（gly）（phen）]·（H2O）2]2·2OH·SO4·4H2O（7）, have been synthesized andcharacterized （bdc=benzenedicarboxylate dianions,pydc=2,5-Pyridinedicarboxylic acid,phen=Phenanthroline, py=pyridine,gly=Glycine acid cation）.The composition,crystalstructures,morphylogies,sizes and properties of the complexes have been studied byElemental analysis（EA）, Fourier transform infrared spectrum（FTIR）, Thermal analysis（DSC-TGA）, X-ray single crystal diffraction（XRD） and Fluorescnce spectrophotometer（FS）,respectively. Structure data is not reported for complexes1⁷.The main content as follows:（1） The complexes [Co（bdc）（py）2]n（1） and [Cu（bdc）（py）2]n（2） were synthesized bysolvent diffusion method.The results showed that the crystal structure of （1） belongs tomonoclinic,space group C2/c with a=2.6718（9）nm,b=1.0122（6）nm, c=2.4762（2） nm,=90°,β=96.421（8）°, γ=90°, V=6.6553（8）nm3, Dx=1.522mg/m3, Mr=381.24, Z=8,F（000）=3120.Single crystal structure analysis of the complexes for one dimensional chain structure.Theresults showed that the crystal structure of （2） belongs to monoclinic,space group P2（1）/nwith a=1.0017（5）nm,b=1.1358（6）nm,c=1.7014（7）nm,=90°,β=114.38（2）°,γ=90°,V=1.7631（15）nm3,Dx=1.454mg/m3, Z=4, Mr=385.85, F（000）=788.0.The complexes are two-dimensional wireless network structure.（2） The complexes [Mn（bdc）（phen）]n（3） and [Cd（bdc）（phen）]n（4） were synthesized byhydrothermal condition.Both of the complexes were monoclinic.Space group P2/c. Theresults showed that the crystal structure of （3） with a=0.8210（8）nm,b=1.0402（4）nm,c=1.879 3（1）nm,=90.0°,β=100.25（60）°,γ=90.0°,V=1.579（5）nm3,Z=4,Dx=1.679mg/m3,μ=0.868mm-1,Mr=399.26,F（000）=812.The structure is one dimensional infinite linear structure.Itsfluorescence better than that of the ligands. The results showed that the crystal structure of（4） with a=0.8228（6）nm,b=1.0579（3）nm,c=1.8899（7）nm,=90.0°,β=100.75（50）°,γ=90.0°,V=1.616（4）nm3,Z=4,Dx=1.877mg/m3,μ=1.383mm-1,Mr=456.72,F（000）=904.It is also onedimensional infinite linear structure.（3） The complexes {[Co（pydc）·（H2O）2]·0.5H2O}n（5） and {[Ni（pydc）·（H2O）3]·H2O}n（6）were synthesized by warm hydrothermal condition, they are triclinic,space group P.The results showed that the crystal structure of （5） with a=0.7234（8）nm, b=0.7328（9）nm,c=1.0027（9）nm,=87.4380（10）°,β=71.5170（10）°,γ=65.3170°,V=0.4557（7）nm3,Dx=2.026mg/m3,μ=1.906mm-1，Mr=456.72，Z=2,F（000）=282.The results showed that the crystal structureof （6） with a=0.699（6）nm,b=0.8223（6）nm,c=0.9505（5）nm,=92.277（2）°,β=99.065（2）°,γ=107.540（2）°,V=0.5501（9）nm3,Dx=1.895mg/m3,Mr=313.89,Z=2,F（000）=324.Two complexesare also the action of the three-dimensional supramolecular in the hydrogen bond formation.（4） The complex [Zn（gly）（phen）·（H2O）2]2·2OH·SO4·4H2O（7） were synthesized byaqueous solution. The results showed that the crystal structure of （7） belongs to triclinic.Space group P with a=1.17163（9）nm,b=1.28022（10）nm,c=1.34849（10）nm,=74.4800°,β=85.4240°,γ=69.8070°,V=1.8289（2）nm3,Z=2,Dx=1.661mg/m3,μ=1.455mm-1,Mr=385.85,F（000）=946.The effect of hydrogen bond formation of the three dimensional networkstructure.The complexes of fluorescence is obviously higher than that of the two ligands.（5） Thermal stabilities of the coordination polymers（2）⁷ have been studied. Theapparent activation energy Ea and the most probable mechanism function G（α） were obtained.And the pre-exponential factor A was obtained on the basis of Ea and G（α）.