Tamayo Abel, Casabó Jaume, Escriche Lluís, González Pablo, Lodeiro Carlos, Rizzi Alberto C, Brondino Carlos D, Passeggi M C G, Kivekäs Raikko, Sillanpää Reijo
Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
Inorg Chem. 2007 Jul 9;46(14):5665-72. doi: 10.1021/ic700375d. Epub 2007 Jun 12.
The properties of Cu(II) and Co(II) complexes with oxygen- or nitrogen-containing macrocycles have been extensively studied; however, less attention has been paid to the study of complexes containing sulfur atoms in the first coordination sphere. Herein we present the interaction between these two metal ions and two macrocyclic ligands with N2S2 donor sets. Cu(II) and Co(II) complexes with the pyridine-containing 14-membered macrocycles 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L) and 7-(9-anthracenylmethyl)-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) have been synthesized. The X-ray structural analysis of {[Co(ClO4)(H2O)(L)][Co(H2O)2(L)]}(ClO4)3 shows two different metal sites in octahedral coordination. The EPR spectra of powdered samples of this compound are typical of distorted six-coordinated Co(II) ions in a high-spin (S=3/2) configuration, with the ground state being S=1/2 (g1=5.20, g2=3.20, g3=1.95). The EPR spectrum of Cu(ClO4)(L) was simulated assuming an axial g tensor (g1=g2=2.043, g3=2.145), while that of Cu(ClO4)(L1) slightly differs from an axial symmetry (g1=2.025, g2=2.060, g3=2.155). These results are compatible with a Cu(II) ion in square-pyramidal coordination with N2S2 as basal ligands. Single-crystal EPR experiment performed on Cu(ClO4)(L1) allowed determining the eigenvalues of the molecular g tensor associated with the copper site, as well as the two possible orientations for the tensor. On the basis of symmetry arguments, an assignment in which the eigenvectors are nearly along the Cu(II)-ligand bonds is chosen.
含氧化或含氮大环的铜（II）和钴（II）配合物的性质已得到广泛研究；然而，对于第一配位层中含有硫原子的配合物的研究较少受到关注。在此，我们展示了这两种金属离子与两个具有N₂S₂供体集的大环配体之间的相互作用。已合成了含吡啶的14元大环3,11 - 二硫杂 - 7,17 - 二氮杂双环[11.3.1]十七碳 - 1(17),13,15 - 三烯（L）和7 - (9 - 蒽基甲基) - 3,11 - 二硫杂 - 7,17 - 二氮杂双环[11.3.1]十七碳 - 1(17),13,15 - 三烯（L1）的铜（II）和钴（II）配合物。{[Co(ClO₄)(H₂O)(L)][Co(H₂O)₂(L)]}(ClO₄)₃的X射线结构分析表明在八面体配位中有两个不同的金属位点。该化合物粉末样品的电子顺磁共振（EPR）谱是高自旋（S = 3/2）构型中畸变六配位钴（II）离子的典型谱，基态为S = 1/2（g₁ = 5.20，g₂ = 3.20，g₃ = 1.95）。Cu(ClO₄)(L)的EPR谱假设为轴向g张量（g₁ = g₂ = 2.043，g₃ = 2.145）进行模拟，而Cu(ClO₄)(L1)的EPR谱与轴对称略有不同（g₁ = 2.025，g₂ = 2.060，g₃ = 2.155）。这些结果与以N₂S₂作为基础配体的四方锥配位中的铜（II）离子相符。对Cu(ClO₄)(L1)进行的单晶EPR实验能够确定与铜位点相关的分子g张量的本征值以及张量的两种可能取向。基于对称性论证，选择本征向量几乎沿着Cu（II） - 配体键的一种归属。
