| In the last decades, considerable efforts have been made the molecule-based magnets. Due to their own characteristics and functions to act as the information recording, magnetic indicator, aerospace and microwave material, the low-dimensional and the high-dimensional molecular-based magnets have attracted considerable interest and become one of the subjects of intensive research.It has great challenge to designing and synthesizing the molecular-based magnets at present. As the better groups, cyano-bridged and azido-bridged complex play an important role.In this dissertation, two cyano-bridged complexes,one non-bridged cyano complex and one non-bridged azido complex have been obtained by reactions of (CN-)and (N3-)with organic ligand (en, pn, phen) and transition-metal ions by using diffusion method in solution. The synthetic methods,materials and physical techniques of four complexes have been reviewed in detail, and all of them were characterized by Elemental Analysis, IR and X-ray powder diffraction. Crystal structure and coordination forms of them were studied systematically by X-ray single crystal diffraction.(1) Two cyano-bridged one-dimensional chain-like nickel complex {[Ni(en)2][Ni(CN)4]}n (complex 1) and [Ni(en)2][Ni(CN)4]·3.5H2O (complex 2) have been synthesized by basic unit ([Ni(CN)4]/2-) and organic ligand (en).The crystals of complex 1 are monoclinic space group P2(1)/C with the cell parameter of a=7.0917(4)A, b=10.6629(5)A, c=9.4975(5)A,α=γ=90°,β=108.196(3)°, V=682.27 (6) A3, Z=4, Dc=1.663 Mg/m3. The structure of complex 1 consists of alternating [Ni(en)2]2+ and [Ni(CN)4]2-fragments linked by two cyanide ligands in a wave fashion. One [Ni(en)2]2+ unit is linked by two cyano nitrogen atoms in a trans configuration via bridging cyano groups to produce a one-dimensional chain-like structure.The crystals of complex 2 are Orthorhombic space group Pnna with the cell parameter of a=28.151(3)A,b=8.3946(8)A, c=14.5441(13)A,α=β=γ=90°, V=3437.0(5)A3, Z=8, Dc=1.564 Mg/m3. The structure of complex 2 consists of alternating [Ni(en)2]2+ in alternant cis-form, trans-form and [Ni(CN)4]2- in cis-form. The complex owns the alternant cis-Ni(en)2, cis-(NC)2Ni (CN)2,trans-Ni(en)2 and cis-(NC)2Ni(CN)2 structure.(2) The complex 1 and complex 2 have been synthesized by using the same materials, method in different conditions which both are different structure. We compared the crystal morpholopy, IR spectrums and XRD of two complexes, a further study on the structure influence of complexes according temperatures and solvents. Studies shows:the synthesis conditions of complex 1 are methanol in 30℃, the synthesis conditions of complex 2 are water and methanol in 10℃.(3) A non-bridged azido manganese complex Mn(phen)2(N3)2 (complex 3) have been synthesized by basic unit (N3-) and organic ligand (phen). The crystals of complex 3 are Triclinic space group Pi with the cell parameter of a=8.1460(5) A,b=11.1290(7)A, c=12.6320(8)A, a=83.6280(10)°,β=82.2170(10)°,γ=73.604 (2)°, V=1085.29(12)A3, Z=2, Dc=1.519Mg/m3. The complex is a neutral complex with non-bridged.(4) A non-bridged cyano nickel complex [Ni(pn)3][Ni(CN)4] (complex 4) have been obtained by basic unit (CN-) and organic ligand (pn). The crystals of complex 4 are Orthorhombic space group Pnna with the cell parameter of a=9.7807(17) A,b=13.3881(2)A, c=16.388(3)A,α=β=γ=90°, V=2144.7(6)A3, Z=8, Dc=1.375Mg/m3. The structure of complex 4 consists of [Ni(pn)3]2+ and [Ni(CN)4]2- as free ion having non-bridged.
|
PDF Full Text Request