Construction of Nano Strucutures Based on Metal Cluster Complexes and Their Chemistry

基于金属簇配合物的纳米结构的构建及其化学

基本信息

批准号：
14340203
负责人：
ITO Tasuku
金额：
$ 10.62万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

Main results are classified into three groups.A.Oligomers of triruthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<n+>.We found the existence of"Charge Transfer Isomer"in the asymmetric mixrd valence state of the pyrazine bridged cluster dimer, and studied their dynamic behavior in intramolecular elecron transfer by means of IR spectro-electrochemical method. The fact that"charge transfer isomers"exist in a single oxidation statte of mixed valence state is extremely rare. Rate constants of intramolecular electron transfer within each isomer, which results in the interconversion of the charge transfer isomer, were on the IR time scale. These results have been published in Angew.Chem.Int., 43, 1376-1381 (2004).We prepared linear oligomers of the cluster, pyrazine bridged trimer and tetramer. These oligomers were designed specifically to show multiple one electron reversible redox waves in their cyclic voltammograms. The trimer and tetramer showed, respecively, 11-step/12-electron and 14-step/15= … More electron reversible redox waves. These results have been published in Bull.Chem.Soc.Jpn.,78,591-598(2005).B.Use of Pt(II)to metal dative bond,Previously we had reported that carbon donor ligands exerted strong ligand field for platinum(II) ion, and that such platinum(II)complexes often form strong platinum to metal dative bonds. Using this idea, we prepared many of nano-sized cluster complexes with the platinum to metal dative bond. Typical examples are a tetranuclear platinum-rhodium-rhodium-platinum cluster complex and a one dimensional linear complex in which silver(I) and platinum(II) are alternately arranged. Manuscript of this study for publication is in preparation.C.Use of metal cluster forming ligand.We found in this study that p-tert-butyl-thiacalix[6]arene and p-tert-butyl-sulfonylcalix[4]arene act as cluster forming ligand. p-tert-butyl-sulfonylcalix[4]arene reacted with an excess of copper acetate to give a nano-sized decacopper cluster complex. And we found that a ferromagnetic interzcton operated in this cluster. This has been published in J.Am.Chem.Soc.,124,11274(2002). p-Tert-butyl-sulfonylcalix[4]arene reacted with lanthanoide ions to afford nano-sized compound with wheel like structure which sonsists of eight lanthanoide ions and four callixarene ligands. This study has been published in Angew.Chem.Int.,43,1382-1385(2004). Less

主要结果分为三组。 “电荷转移异构体”存在于混合价状态的单个氧化词中，这一事实极为罕见。在每个异构体内分子内电子转移的速率常数，这会导致电荷转移异构体的相互转换，为IR时间尺度。这些结果已发表在Angew.chem.int。，43，1376-1381（2004）中。我们准备了群集，吡嗪桥梁的三聚体和四聚体的线性低聚物。这些低聚物专门设计用于在其环状伏安图中显示多个电子可逆的氧化还原波。三聚体和四聚体，特别是11步/12电子和14步/15 =…更多的电子可逆氧化还原波。这些结果已发表在Bull.Chem.Soc.jpn。，78,591-598（2005）.b。将Pt（II）与金属键使用使用，以前我们报道说，碳供体配体为铂（II）离子（II）ION和这种铂（II）配合物通常形成了强型铂型甲状腺素的碳含量强的配体。使用这个想法，我们将许多纳米大小的簇配合物与铂构成了金属差分键。典型的例子是四核铂r-rhodium-platinum platinum簇复合物和一个维度线性复合物，其中银（I）和铂（II）被安排。本研究的手稿正在制备中。 p-tert叔丁基 - 磺基calix [4]芳烃与过量的乙酸铜反应，从而产生了纳米大小的decapper簇复合物。我们发现在该群集中运行的铁磁Interzcton。这已发表在J.Am.Chem.Soc。，124,11274（2002）中。 p-tert-butyl-sulfonylcalix [4]芳烃与灯笼离子反应，提供纳米大小的化合物，带有轮子，例如结构，这些化合物的儿子是八个兰萨诺德离子和四个Callixarene配体的儿子。这项研究已发表在Angew.chem.int。，43,1382-1385（2004）中。较少的