Preparation of Nano-sized Transition Metal Complexes and Their Chemical Functions

主要研究结果如下：A.氧化还原活性三钌簇[Ru_3（O）（CH_3COO）_6L_3]^<n+>的线性低聚物。我们在氧化还原化学领域的技术书籍“Redox Systems Under Nano-Space Control”（Springer，2006）中发表了三钌簇的线性低聚物的氧化还原性质。在这本书中报道的化合物是专门设计的，在它们的循环伏安图中显示多步一电子可逆氧化还原波。混合价异构体：我们制备了两个以2-甲基吡嗪为桥连的不对称混合价簇合物[Ru_3（O）（CH_3COO）_6L_3]^<nn+>。用红外光谱电化学方法研究了这些化合物分子内电子转移的动力学行为。结果表明，在各混价化合物的单一氧化斯塔特态中存在着“混价异构体”，各异构体分子内电子转移速率常数随氧化时间的延长而增大，从而导致了各异构体之间的相互转化 关于我们 电荷转移异构体，在IR时间标度上（J. Am.化学会，127，2382-2383（2005））.C Ferromagnetic coupling promoted by k^3N：k^2N bridging system.报道了四种具有相同基序的新型三核配合物[M{Cu（pz_2bg）_2}M]^4+&gt;（M = Cu^<II>4，Ni^<II>4，Co^4，<II>Mn^4<II>）的合成、结构和磁性，其中包括配合物配体[Cu（pz_2bg）_2]（pz_2bg-=二（吡唑脲基）氨基化物;双胍基的双吡唑基衍生物）。所有化合物中的铁磁相互作用都归因于磁性dσ轨道的严格正交性，而磁性d σ轨道是由pz_2bg配体的k^3N：k^2N桥联几何结构控制的（Inorg. Chem.，46，6460-6466（2006））.对叔丁基磺酰基杯[4]芳烃（L^）为簇合物配体，合成了3个四方平面四核簇合物[M_4（L）（AcO）_4（μ_4-OH）]（M=Mn^<II>，Co^<II>，Ni^<II>）<4->。沿着报道了它们的结构和性能。少

Main results are four following studies.A. linear oligomers of redox active trirthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<n+>.We published redox properties of linear oligomers of triruthenium cluster in a technical book of the redox chemistry area, "Redox Systems Under Nano-Space Control" (Springer, 2006). The compounds reported in this book were designed specifically to show multistep-one electron reversible redox waves in their cyclic voltammograms.B. Mixed valence isomers.We prepared two asymmetric mixed valence clusters, dimmers of trirthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<nn+>, bridged by 2-methyl-pyrazine. The dynamic behavior of these compounds concerning intramolecular elecron transfer has been studied by means of IR spectro- electrochemistry. The results show that "mixed-valence isomers" exist in a single oxidation statte of each mixed valent compound, and that rate constants of intramolecular electron transfer within each isomer, which results in the interconversion of the … More charge transfer isomer, were on the IR time scale (J. Am. Chem. Soc., 127, 2382-2383 (2005)).C Ferromagnetic coupling promoted by k^3N : k^2N bridging system.Syntheses, structures and magnetic properties of four novel trinuclear complexes of the same motif [M{Cu(pz_2bg)_2}M]^<4+> (M = Cu^<II>, Ni^<II>, Co^<II>, Mn^<II>), which include the complex ligand [Cu(pz_2bg)_2], are reported (pz_2bg-= di(pyrazolecarbimido)aminate; bis-pyrazolyl derivative of biguanidate). The ferromagnetic interaction operated in all the compounds was ascribed to the strict orthogonality of magnetic dσ orbitals, which are controlled by the k^3N : k^2N bridging geometry of pz_2bg-ligands (Inorg. Chem., 46, 6460-6466 (2006)).D. Tetranuclear cluster complexes supported by a cluster forming ligand, p-tert-butylsulfonylcalix[4]arene.Three square-planar tetranuclear clusters [M_4(L)(AcO) _4 (μ_4-OH)] (M=Mn^<II>, Co^<II>, and Ni^<II>) were synthesized using tetra-anionic p- tert-butylsulfonylcalix[4]arene (L^<4->)as a cluster forming ligand. Their structures and properties are reported along with syntheses. Less