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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

主要结果分为三类：A.三钌簇合物[Ru_3（O）（CH_3COO）_6L_3]^<n+>在吡嗪桥联簇合物的不对称混合价态中发现了“电荷转移异构体“的存在，并用红外光谱-电化学方法研究了它们的分子内电子转移动力学行为。“电荷转移异构体“存在于混合价态的单一氧化斯塔特中的事实是极其罕见的。每个异构体内的分子内电子转移的速率常数，这导致在相互转化的电荷转移异构体，在IR时间尺度上。这些结果已经发表在Angew.Chem.Int.上，43，1376-1381（2004）。我们制备了簇、吡嗪桥连的三聚体和四聚体的线性低聚物。这些低聚物被专门设计为在其循环伏安图中显示多个单电子可逆氧化还原波。三聚体和四聚体分别表现出11-阶/12-电子和14-阶/15-电子， ...更多信息电子可逆氧化还原波。这些结果已发表在Bull. Chem. Soc. Jpn.上，B. Pt（II）与金属配价键的使用，以前我们已经报道了碳供体配体对铂（II）离子施加强配体场，并且这种铂（II）络合物通常形成强的铂与金属配价键。利用这一思想，我们制备了许多具有铂-金属配价键的纳米簇合物。典型的例子是四核铂-铑-铑-铂簇络合物和其中银（I）和铂（II）交替排列的一维线性络合物。C.金属簇形成配体的应用本研究发现对叔丁基硫杂杯[6]芳烃和对叔丁基磺酰基杯[4]芳烃作为金属簇形成配体。对叔丁基磺酰基杯[4]芳烃与过量的乙酸铜反应，得到纳米级的十铜簇合物。我们发现在这个星系团中有一个铁磁性的相互作用。这篇文章发表在《美国化学会杂志》上，124，11274（2002）。对叔丁基磺酰基杯[4]芳烃与稀土离子反应，得到了由八个稀土离子和四个杯芳烃配体组成的具有轮状结构的纳米化合物。这项研究已发表在Angew.Chem.Int.上，43，1382 -1385（2004）中描述的。少