Some Transition Metal Coordination Polymer Synthesis And Structural Characterization

The research on transition metal coordination polymers not only connects inorganic and organic chemistry but also involves basic theory and applications. In recent years, this field has become one of the international frontiers among inorganic chemistry, crystallization chemistry and materials chemistry and is currently rapidly expanding. This thesis focuses mainly on the assembly of low-dimensional building blocks into one-, two-, or three-dimensional coordination polymers via various intermolecular interactions such as coordinate bonding, hydrogen bonding, - stacking and electrostatic interactions.Two kinds of metal-organic coordination polymers and a novel Waugh-type isopolyoxometalate, namely [Co(4,4'-bipy)(H2O)4] (4-abs)2 H2O (4,4'-bipy = 4,4'-bipyridine, 4-abs = 4-aminobenzene sulfonate) (1) , [Mn(4,4'-bipy)(H2O)4][4-abs]2-4H2O (2), [Fe2 Fe O2 (C6H4NO2)2(C2O4)] (IN = isonicotinate) (3), [Zn(IN)2(H2O)4] (4), and Na4Mo10O32 8H2O (5), have been synthesized by the normal and hydrothermal techniques, and structurally characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, electron paramagnetic resonance spectra, thermogravimetric analysis, and X-ray photoelectron spectra. Complexes (1) and (2) both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite chains. The 4-abs anions in (1) form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4'-bipy)(H2O)4]2+ linear covalently bonded chains are located. Complex (2) contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4'-bipy)(H2O)4]2+ linear covalentchains exist in these channels. Complex (3) exhibits a 3-D covalently bonded pillared network structure consisting of three mixed-valence Fe centers, one oxalate anion, and two isonicotinate anions. Complex (4) possesses a 3-D supramolecular network formed via extensive hydrogen bonding interactions. Further, a novel Waugh-type decamolybdate Na4Mo10O32-8H2O (5) has been synthesized and its crystal structure has been determined, which is the first Waugh-type isopolyoxometalate.