Trinuclear Heterobimetallic Ni2Ln complexes [L2Ni2Ln][ClO4] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er; LH3 = (S)P[N(Me)N
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- 作者：Vadapalli Chandrasekhar ; Balasubramanian Murugesa Pandian ; Ramamoorthy Boomishankar ; Alexander Steiner ; Jagadese J. Vittal ; Ahmad Houri ; Rodolphe Clé ; rac
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：June 2, 2008
- 年：2008
- 卷：47
- 期：11
- 页码：4918 - 4929
- 全文大小：3650K
- 年卷期：v.47,no.11(June 2, 2008)
- ISSN：1520-510X
文摘
The reaction of LH3 with Ni(ClO4)2·6H2O and lanthanide salts in a 2:2:1 ratio in the presence of triethylamine leads to the formation of the trinuclear complexes [L2Ni2Ln][ClO4] (Ln = La (2), Ce (3), Pr (4), Nd (5), Sm (6), Eu (7), Gd (8), Tb (9), Dy (10), Ho (11) and Er (12) and L: (S)P[N(Me)N
CH−C6H3-2-O-3-OMe]3). The cationic portion of these complexes consists of three metal ions that are arranged in a linear manner. The two terminal nickel(II) ions are coordinated by imino and phenolate oxygen atoms (3N, 3O), whereas the central lanthanide ion is bound to the phenolate and methoxy oxygen atoms (12O). The Ni−Ni separations in these complexes range from 6.84 to 6.48 Å. The Ni−Ni, Ni−Ln and Ln−Ophenolate bond distances in 2−12 show a gradual reduction proceeding from 2 to 12 in accordance with lanthanide contraction. Whereas all of the compounds (2−12) are paramagnetic systems, 8 displays a remarkable ST = 11/2 ground state induced by an intramolecular Ni· · ·Gd ferromagnetic interaction, and 10 is a new mixed metal 3d/4f single-molecule magnet generated by the high-spin ground state of the complex and the magnetic anisotropy brought by the dysprosium(III) metal ion.
CH−C6H3-2-O-3-OMe]3). The cationic portion of these complexes consists of three metal ions that are arranged in a linear manner. The two terminal nickel(II) ions are coordinated by imino and phenolate oxygen atoms (3N, 3O), whereas the central lanthanide ion is bound to the phenolate and methoxy oxygen atoms (12O). The Ni−Ni separations in these complexes range from 6.84 to 6.48 Å. The Ni−Ni, Ni−Ln and Ln−Ophenolate bond distances in 2−12 show a gradual reduction proceeding from 2 to 12 in accordance with lanthanide contraction. Whereas all of the compounds (2−12) are paramagnetic systems, 8 displays a remarkable ST = 11/2 ground state induced by an intramolecular Ni· · ·Gd ferromagnetic interaction, and 10 is a new mixed metal 3d/4f single-molecule magnet generated by the high-spin ground state of the complex and the magnetic anisotropy brought by the dysprosium(III) metal ion.