Abstract
A series of Mn citrate coordination polymers [NaMn(Hcit)] n ( 1, H 4cit = citric acid), [MnCa 2(Hcit) 2(H 2O) 4] n ( 2), [{Mn(Hcit)(H 2O) 2} 2Mn(H 2O) 4] n ( 3) and [{Mn(Hcit)(H 2O) 2} 2Mn(H 2O) 2] n ( 4) have been synthesized by the solvothermal method and the conventional solvent method. 1 and 2 represent novel examples of bimetallic Mn citrate complexes with 3-D architectures. In the structure of 1, Mn(μ-O) 3Na and Mn(μ-O)(μ-OCO)Na units are alternately fused via edge-sharing to form Mn…Na…Mn chains and the citrate trianion links between the chains by terminal carboxylate groups. In the structure of 2 the Ca ions are correlated by carboxylate bridges to create a two-dimensional Ca-citrate layer at the a-c face and the Mn(II) ions form a helix chain along the a axis by carboxylate bridges. Each citrate trianion links 9 and 8 hetero-metal ions in 1 or 2, respectively, through component carboxylate and hydroxyl groups. In 3 and 4 both the Mn(Hcit)(H 2O) 2 units are coupled to form centrosymmetrical dimer units, which construct the one-dimensional chain structure of 3 and the 3D network architecture of 4. Infrared spectra and the magnetic properties are also discussed, being associated with the bridging coordination mode of the carboxylate group.
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