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標題: Linear Tetranickel String Complexes with Mixed Supported Ligands and Mixed-Valence Units Ni-2 (3+): Synthesis, Crystal Structure, and Magnetic Studies
作者: Yeh, C.W.
Liu, I.P.C.
Wang, R.R.
Yeh, C.Y.
Lee, G.H.
Peng, S.M.
關鍵字: Molecular wire;Mixed-valent compounds;Magnetic properties;Nickel;Ligand effects;theoretical-analysis;quantum-mechanics;new-generation;metal;chain;dipyridylamide;wires;cu
Project: European Journal of Inorganic Chemistry
期刊/報告no:: European Journal of Inorganic Chemistry, Issue 20, Page(s) 3153-3159.
The synthesis, crystal structures, and magnetic properties of linear tetranickel string complexes supported by mixed 2-(alpha-pyridylamino)-1,8-naphthyridine (Hpyany) and N-(p-tolylsulfonyl)dipyridyldiamine (H(2)tsdpda) ligands are reported. In comparing the crystal structure of [Ni-4(pyany)(2)(tsdpda)(2)Cl] (1) with that of [Ni-4(pyany)(2)(tsdpda)(2)Cl(H2O)[(PF6) (2), the one-electron-reduced compound 1 displays shorter Ni(3)-Ni(4) (ca. 2.28 angstrom) and longer Ni(3)-N (ca. 2.02 angstrom) bond lengths. Similar trends have also been observed for axial NCS--substituted derivatives [Ni-4(pyany)(2)(tsdpda)(2)(NCS)] (3) and [Ni-4(pyany)(2)(tsdpda)(2)(NCS)(2)] (4). These structural variations indicate the formation of a mixed-valence [Ni-2](3+) unit and a three-electron, two-center Ni(4)-Ni(3) a bond. Magnetic measurements of 2 and 4 show that both terminal Ni(1) and Ni(4) ions are in the high-spin states (S = 1) and are antiferromagnetically coupled. The one-electron-reduced complexes 1 and 3, however, exhibit a delocalized mixed-valence [Ni-2](3+) unit (S = (3)/(2)), which is antiferromagnetically coupled with the terminal high-spin Ni-II ion.
ISSN: 1434-1948
DOI: 10.1002/ejic.201000145
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