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

纳米过渡金属配合物的制备及其化学功能

基本信息

批准号：
17550052
负责人：
ITO Tasuku
金额：
$ 1.34万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

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

主要成果有以下四项研究：A.氧化还原活性三钌团簇的线性低聚物[Ru_3(O)(CH_3COO)_6L_3]^<n+>。我们在氧化还原化学领域的技术书籍中发表了三钌团簇线性低聚物的氧化还原性质，“纳米空间控制下的氧化还原系统”（Springer，2006）这本书中报道的化合物专门设计用于显示多步电子可逆。 B. 混合价异构体。我们制备了两个不对称混合价簇，三铼簇的二聚体[Ru_3(O)(CH_3COO)_6L_3]^<nn+>，由2-甲基吡嗪桥接。通过红外光谱电化学研究了这些化合物在分子内电化学方面的行为。表明“混合价异构体”存在于每种混合价化合物的单一氧化态中，并且每种异构体内分子内电子转移的速率常数（导致电荷转移异构体的相互转化）在红外时间上(J. Am. Chem. Soc., 127, 2382-2383 (2005)).C 铁磁耦合促进k^3N : k^2N 桥接系统。具有相同基序的四种新型三核配合物的合成、结构和磁性 [M{Cu(pz_2bg)_2}M]^<4+> (M = Cu^<II>,据报道，Ni^<II>、Co^<II>、Mn^<II>) 包括络合物配体 [Cu(pz_2bg)_2] (pz_2bg-=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，该轨道由 pz_2bg- 的 k^3N : k^2N 桥接几何结构控制。配体（无机化学，46, 6460-6466 (2006)).D. 由簇形成配体对叔丁基磺酰基杯[4]芳烃支持的四核簇配合物。三个方形平面四核簇 [M_4(L)(AcO) _4 (μ_4-OH)] (M =Mn^<II>、Co^<II> 和 Ni^<II>) 使用四阴离子 p- 合成叔丁基磺酰杯[4]芳烃(L^<4->)作为簇形成配体，其结构和性质与合成一起报道。