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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.三钌簇低聚物[Ru_3(O)(CH_3COO)_6L_3]^<n+>。我们在吡嗪桥连簇二聚体的不对称混合价态中发现了“电荷转移异构体”的存在，并通过红外光谱研究了它们在分子内电子转移中的动态行为。光谱电化学方法。 “电荷转移异构体”以混合价态的单一氧化态存在的事实是极其罕见的。每个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）位于红外时间尺度上。这些结果发表在Angew.Chem.Int., 43, 1376-1381 (2004)上。我们制备了簇的线性低聚物、吡嗪桥联三聚体和四聚体。这些低聚物经过专门设计，可在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显示出 11 步/12 电子和 14 步/15=…更多电子可逆氧化还原波。这些结果发表在Bull.Chem.Soc.Jpn.,78,591-598(2005).B.Use of Pt(II)to metal配位键，之前我们报道过碳供体配体对铂(II)离子产生强配体场，并且这种铂(II)配合物经常形成强的铂与金属配位键。利用这个想法，我们制备了许多具有铂与金属配位键的纳米级簇配合物。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。本研究的出版手稿正在准备中。C.金属簇形成配体的使用。我们在本研究中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，得到纳米尺寸的十铜簇络合物。我们发现铁磁相互作用子在这个星团中运行。这已发表在 J.Am.Chem.Soc.,124,11274(2002) 上。对叔丁基磺酰基杯[4]芳烃与镧系元素离子反应得到具有轮状结构的纳米化合物，该化合物由八个镧系元素离子和四个杯芳烃配体组成。这项研究发表在Angew.Chem.Int.,43,1382-1385(2004)上。较少的