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

主要研究结果如下：氧化还原活性氚簇的线性低聚物[Ru_3(O)(CH_3COO)_6L_3]^<n+>。我们在氧化还原化学领域的技术书籍《纳米空间控制下的氧化还原系统》中发表了三钌簇线性低聚物的氧化还原特性（施普林格，2006）。在这本书中报告的化合物被专门设计为在其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。以2-甲基吡嗪为桥接剂，制备了两种不对称混合价簇，即三氮团簇[Ru_3(O)(CH_3COO)_6L_3]^<nn+>的二聚体。用红外光谱电化学方法研究了这些化合物的分子内电子转移动力学行为。结果表明，“混价异构体”在每一种混价化合物中均以单一的氧化态存在，各异构体内的分子内电子转移速率常数在IR时间尺度上均达到较高的水平(J. m.；化学。Soc。[3] . k^3N: k^2N桥接体系促进铁磁耦合。报道了四种新型三核配合物[M{Cu(pz_2bg)_2}M]^<4+> (M = Cu^<II>, Ni^<II>, Co^<II>, Mn^<II>)的合成、结构和磁性能，包括配合体[Cu(pz_2bg)_2] (pz_2bg-= di（pyrazolecarbimido）胺酸酯；双胍的双吡唑衍生物)。所有化合物的铁磁相互作用都归因于磁dσ轨道的严格正交性，这是由pz_2bg配体的k^3N: k^2N桥接几何结构控制的。化学。[j] .地球科学进展，2016,33(2):1 -6。由簇形成配体对叔丁基磺酰基杯芳烃支持的四核簇状配合物。以四阴离子对叔丁基磺酰基杯[4]芳烃（L^<4->）为配体合成了3个方形平面四核簇[M_4(L)(AcO) _4(μ_4-OH)] （M=Mn^<II>, Co^<II>和Ni^<II>）。报道了它们的结构和性质以及合成方法。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