Mn(II) Coordination Polymers Based on Bi-, Tri-, and Tetranuclear and Polymeric Chain Building Units: Crystal Structures and Magnetic Properties

Five new Mn(II) coordination polymers, namely Mn(2)(tbip)(2)(bix)] (1), Mn(3)(tbip)(3)(bix)(2)] (2), Mn(3)(tbip)(2)(Htbip)(2)(bib)(2)]·4H(2)O (3), Mn(4)(tbip)(4)(bbp)(2)(H(2)O)(2)] (4), and Mn(4)(tbip)(4)(bip)]·2H(2)O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H(2)tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear Mn(2)O(2)] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear Mn(3)(COO)(6)] units. Complex 3 shows a 3D pcu net based on trinuclear Mn(3)(COO)(6)] clusters as nodes. Complex 4 features a 3D 8-connected structure constructed from the distorted square-grid tetranuclear Mn(4)(μ(2)-COO)(8)(μ(2)-H(2)O)] units. Complex 5 shows a 3D (4,5,6)-connected net containing 1D μ-O/μ-COO alternately bridged chains. Magnetic susceptibility measurements indicate that complexes 1 and 3-5 show weak antiferromagnetic interactions between the adjacent Mn(II) ions, whereas 2 is a three-spin center homometallic ferromagnetic system.