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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

主要结果可分为三类：a .三钌簇的低聚物[Ru_3(O)(CH_3COO)_6L_3]^<n+>；在吡嗪桥簇二聚体的不对称混价态中发现了“电荷转移异构体”的存在，并利用红外光谱电化学方法研究了其分子内电子转移的动力学行为。“电荷转移异构体”存在于单一氧化态或混合价态的情况极为罕见。各异构体分子内电子转移速率常数均在红外时标上，这导致了电荷转移异构体的相互转化。这些研究结果发表在《生物化学》杂志上。生态学报，43,1376-1381（2004）。我们制备了聚类、吡嗪桥接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步/12电子和14步/15=…的电子可逆氧化还原波。研究结果发表在《化学学报》，78,591-598（2005）。利用Pt（II）与金属的结合键，以前我们报道过碳供体配体对铂（II）离子施加强配体场，并且这种铂（II）配合物通常形成强铂与金属的结合键。利用这一思路，我们制备了许多具有铂-金属键的纳米级簇状配合物。典型的例子是四核铂-铑-铑-铂簇配合物和银(I)和铂（II）交替排列的一维线性配合物。论文正在准备中。c .金属簇形成配体的使用。本研究发现对叔丁基-硫杯[6]芳烃和对叔丁基-磺酰基杯[4]芳烃是簇形成配体。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十铜簇配合物。我们发现一个铁磁夹层在这个团簇中起作用。这已经发表在j.a.m chem . soc .,124,11274（2002）。对叔丁基磺酰基杯芳烃与镧系离子反应得到了由8个镧系离子和4个杯芳烃配体组成的轮状纳米化合物。该研究已发表于《生物化学杂志》，43,1382-1385（2004）。少