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Chemical Functions of Transition Metal Assembled Complexes

过渡金属组装配合物的化学功能

基本信息

批准号：
10149102
负责人：
ITO Tasuku
金额：
$ 49.66万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas (A)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10149102/
关键词：
redox behavior mixed valence multilayered complex proton coupled electron transfer multi-step electron transfer transition metal assembled complexes 可逆的結晶構造変化多サイト反応場

项目摘要

Ito, using infrared spectral lineshape analysis in conjunction with infrared spectroelectrochemistry, determined the rates of intermolecular electron transfer between triruthenium cluster units in mixed valence complexes. The electron transfer rates along a "non symmetric potential energy surface" were elucidated and multiple electron transfer pathways and rates in a bridged cluster trimer were identified. As well as the electronic properties of cluster complexes, methods for assembling extended structures were examined. Using Pt complexes coordinated by high field ligands, strong unsupported Pt->M dative bonds were prepared, and when the Pt complexes were reacted with Ag ion or Rh dimers, linear and large multinuclear complexes were isolated.Sasaki examined two areas: ligand-metal interactions and the synthesis of large complexes. In the first project, the stability of mixed valence states formed by ligand based redox processes were studied, and it was discovered that, when the metal … More centers and ligands mutually form mixed valence states, a "double mixed valence state" exists. In the second area hexanuclear rhenium complexes with new multidentate units were prepared and the structure of a rhenium hexamer having six large pyridylporphyrin ligands was determined.Nishihara's research involved induced structural changes in transition metal complexes. Azo-conjugated transition metal complexes undergo a reversible trans-to-cis isomerization upon concomitant irradiation with a single UV light source and oxidation of the metal. Protonation of a ヲミ-conjugated ferrocene-anthraquinone system caused intermolecular electron transfer to occur. This leads to a novel structural change creating an ヲヌ^6-fulvene-cumulene Fe(II) complex. The structure of the proton attached complex and the properties of the unusually fluxional complex were elucidated.Haga prepared multilayered metal complexes on a solid electrode through layer-by-layer growth. As well, a two-dimensional coordination system was developed at the air-water interface using Langmuir-Blodgett techniques.Fujita furthered his research involving the construction of 2-D and 3-D complexes using 2,4,6-tris(4-pyridyl)triazine as a bridging ligand. An interesting 3-D network, which undergoes a reversible structural change in the solid state upon absorption/desorption of a guest molecule, was prepared. Less

Ito利用红外谱线形状分析与红外光谱电化学相结合，确定了混合价配合物中三钌簇单位之间的分子间电子转移速率。研究了“非对称势能面”上的电子转移速率，确定了桥接簇三聚体中的多种电子转移途径和速率。除了团簇配合物的电子性质外，还研究了组装扩展结构的方法。利用高场配体配位的Pt配合物制备了强无负载Pt->M负性键，当Pt配合物与Ag离子或Rh二聚体反应时，分离出线性和大的多核配合物。佐佐木研究了两个领域：配体与金属的相互作用和大型配合物的合成。在第一个项目中，研究了基于配体的氧化还原过程形成的混合价态的稳定性，发现当金属…More中心和配体相互形成混合价态时，存在“双混合价态”。在第二领域，制备了具有新的多齿单元的六核铼配合物，并确定了具有六个大吡啶卟啉配体的铼六聚体的结构。西原的研究涉及过渡金属配合物的诱导结构变化。偶氮共轭过渡金属配合物在单一紫外光源照射和金属氧化的同时发生可逆的反式到顺式异构化。偶联二茂铁-蒽醌体系的质子化引起了分子间的电子转移。这导致了一种新的结构变化，产生了一个u - u ^6-fulvene- culculene Fe（II）配合物。阐明了质子附着配合物的结构和异常流动配合物的性质。Haga通过逐层生长在固体电极上制备了多层金属配合物。同时，利用Langmuir-Blodgett技术在空气-水界面建立了二维协调系统。Fujita进一步研究了使用2,4,6-三（4-吡啶基）三嗪作为桥接配体构建二维和三维配合物。制备了一个有趣的三维网络，该网络在客体分子的吸收/解吸后，在固体状态下经历了可逆的结构变化。少