Two Pillared-layer Co(Ⅱ) Metalorganic Frameworks Displaying Pore Modulation by Rodlike Ligands

Two novel compounds, {Co2(epda)2(4,4-bpy)(H2O)2]·3H2O}n1 and {Co2(epda)2(bpe)(H2O)2]3H2O}n2(H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 4,4’-bpy=4,4’-bipyridine and bpe=1,2-di(4-pyridyl)ethylene) were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, therm ogravimetric analysis (TGA), and singlecrystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a=13.344(5), b=14.724(5), c=8.267(3), β=105.840(4)°, V=1562.5(10)3, Dc=1.480 g/cm3, Mr=375.19, Z=4, F(000)=712, μ=1.121 mm-1, the final R=0.0512 and wR=0.1260 for 2890 observed reflections with I>2σ(I). 2 belongs to the monoclinic system, space group P21/c with a=14.224(4), b=14.726(4), c=8.287(2), β=99.696(4)°, V=1711.1(9)3 , Dc=1.402g/cm3, Mr=388.21, Z=4, F(000)=740, μ=1.027 mm-1 , the final R=0.0354 and wR=0.0862 for 12237 observed reflections with I>2σ(I). Both complexes present intimately related structures featuring infinite Co-carboxylate layers of CoⅡ(epda)(H2O)]n pillared by 4,4’-bpy (or bpe) molecule to produce the microporous frameworks, unambiguously indicating that pore dimensions of the framework are regulated by the N,N’-donor pillars.