The polymeric Co（Ⅱ） complex[Co（Hdhpc）（py）]n（1）（py = pyridine,H3dhpc =2,6-dihydroxypyridine-4-carboxyl acid） was prepared and characterized.X-ray diffraction data revealed that the compound crystallizes in dimorphic 1α and 1β forms at room and low temperature,respectively.The former crystallizes in the orthorhombic crystal system,space group Pbcm with a =7.209（1）,b = 14.834（3）,c = 15.376（3） A°,V= 1644.3（5）A°3,Z = 4,C（16）H（13）CoN3O4,Mr = 370.22,Dc= 1.496 g/cm^3,F（000） = 756,μ = 1.068 mm^-1,R = 0.0633 and wR = 0.1192.While 1β is attributed to the monoclinic space group C2/c with a = 32.102（4）,b = 7.022,c = 14.945（2）A°,β = 109.052（5）°,V= 3184.4（6） A°3,Z= 8,Dc= 1.544 g/cm^3,F（000） = 1512,μ = 1.103 mm^-1,R = 0.0428 and wR =0.0797.The conformation changes of pyridines between Co-citrazinate planes leading to a reversible single-crystal to single-crystal transformation.The variable temperature magnetic data indicate a weak ferrimagnetism.
Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.
