Fegy Karine, Luneau Dominique, Belorizky Elie, Novac Miguel, Tholence Jean-Louis, Paulsen Carley, Ohm Thorsten, Rey Paul
Département de Recherche Fondamentale sur la Matière Condensée, Service de Chimie Inorganique et Biologique, Laboratoire de Chimie de Coordination (URA CNRS 1194), CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cédex 09, France, Laboratoire de Spectrométrie Physique (CNRS-UMR 5588), Université Joseph Fourier Grenoble 1, BP 87, 38402 Saint Martin d'Hères Cedex, France, and Centre de Recherche sur les Très Basses Températures, CRTBT-CNRS, BP166, 38042 Grenoble Cedex 09, France.
Inorg Chem. 1998 Sep 7;37(18):4524-4532. doi: 10.1021/ic971619d.
Extended linear complexes of manganese(II) with a bis-chelating nitronyl nitroxide ligand, 2-(2-imidazolato)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-3-oxide-1-oxy (NITIm), have been prepared where metallic and organic spin carriers alternate. Depending on the deprotonating agent, the solvent, and the counteranion, the species [Mn(NITIm)(H(2)O)(2)]CH(3)COO, 1, [Mn(NITIm)(DMSO)(2)]BPh(4), 2, [Mn(NITIm)(H(2)O)(ImH)]NO(3), 3, and [Mn(NITIm)(NITImH)]ClO(4), 4, have been obtained, which differ by the additional ligands completing the metal coordination sphere. Complexes 1-3 are cis isomers and 4 is found as the mer modification; in all compounds, one observes a regular alternation of Lambda and Delta metal environments. Their magnetic properties are similar, with Mn(II)-nitroxide interactions J approximately -45 cm(-)(1) (H = -2JS(i)().S(j)()), and they display weak ferromagnetic properties below 5 K. Canting of the manganese ions is responsible for these properties. Relevant crystallographic parameters are as follows: 1, space group Fdd2, a = 16.713(1), b = 40.111(3), c = 9.735(1), Z = 16; 2, space group Pca2(1), a = 30.328(3), b = 13.422(1), c = 9.589(1), Z = 4; 3, space group P2(1)/c, a = 9.787(2), b = 22.973(5), c = 9.671(2), beta = 117.32(3) degrees, Z = 4; 4, space group P2(1)/c, a = 9.761(2), b = 28.668(5), c = 9.941(2), beta = 96.07(3) degrees, Z = 4.
已制备出锰（II）与双螯合硝酰基氮氧化物配体2-（2-咪唑基）-4,4,5,5-四甲基-4,5-二氢-1H-咪唑基-3-氧化物-1-氧基（NITIm）形成的扩展线性配合物，其中金属和有机自旋载体交替排列。根据去质子化剂、溶剂和抗衡阴离子的不同，得到了配合物[Mn（NITIm）（H₂O）₂]CH₃COO（1）、[Mn（NITIm）（DMSO）₂]BPh₄（2）、[Mn（NITIm）（H₂O）（ImH）]NO₃（3）和[Mn（NITIm）（NITImH）]ClO₄（4），它们因完成金属配位球的额外配体不同而有所差异。配合物1 - 3是顺式异构体，4以面式变体形式存在；在所有化合物中，都观察到Λ和Δ金属环境的规则交替。它们的磁性质相似，锰（II） - 氮氧化物相互作用J约为 - 45 cm⁻¹（H = - 2JSᵢ·Sⱼ），并且在5 K以下显示出弱铁磁性质。锰离子的倾斜导致了这些性质。相关晶体学参数如下：1，空间群Fdd2，a = 16.713（1），b = 40.111（3），c = 9.735（1），Z = 16；2，空间群Pca2₁，a = 30.328（3），b = 13.422（1），c = 9.589（1），Z = 4；3，空间群P2₁/c，a = 9.787（2），b = 22.973（5），c = 9.671（2），β = 117.32（3）°，Z = 4；4，空间群P2₁/c，a = 9.761（2），b = 28.668（5），c = 9.941（2），β = 96.07（3）°，Z = 4。
