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Synthesis of novel metal complexes exhibiting multi-stabilities and creation of molecular systems exhibiting multi-functionalities

具有多稳定性的新型金属配合物的合成和具有多功能性的分子系统的创建

基本信息

批准号：
17205007
负责人：
NISHIHARA Hiroshi
金额：
$ 27.37万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

The purpose of this study is to create intelligent molecular systems where the chemical and physical structures and the optical, magnetic and electronic properties are changed reversibly and then to produce "molecular functional devices" by combining the molecular systems with electrode surface. As for □-conjugated redox complex oligomers and polymers, we have succeeded in bottom-up synthesis of one- and three-dimensional oligomer complex molecular wires by step-wise coordination reactions on the surface, and have found the phenomena of redox-conduction along the molecular wires for the first time. Photo-electron conducting molecular wires were also prepared using such molecular wires with terminal porphyrin moieties. As for photochromic complexes, we synthesized ferrocenylspiropyran with an ability to control the memory depth by changing the redox state, bis(ferrocenylethynyl)ethane and its triarylamine derivatives, which cause alteration of electronic communication between terminal redox moieties by photoisomerization, and self-assembled monolayers of ferrocenylazobenzene, which undergoes reversible isomerization of azobenzene moieties with a single green light source by combining with the redox reaction of ferrocene moiety. As for donor-acceptor conjugated molecules, we have found that 1-ferrocenylethynylanthraquinone reacts with proton to cause cyclization reaction to give a pyrilium salt, which shows valence tautomerization with temperature change. We have also found that 1,4-bis(ferrocenylethynyl)anthraquinone undergoes reversible single crystal - single crystal structural changes by absorption of guest molecules. As for heterometal cluster complexes, we synthesized several types of new cluster complexes by the reaction of metalladithiolenes with metal carbonyls. They exhibit unique redox and optical properties.

本研究的目的是创造化学和物理结构以及光学、磁学和电学性质可逆改变的智能分子体系，然后将分子体系与电极表面相结合来制造分子功能器件。对于氧化还原络合低聚物和聚合物，我们通过表面逐步配位反应，成功地自下而上地合成了一维和三维齐聚物复合分子线，并首次发现了沿分子线的氧化还原电导现象。用这种末端带有卟啉基团的分子导线也制备了光电子导电分子导线。在光致变色化合物方面，我们合成了能够通过改变氧化还原状态来控制存储深度的二茂铁基螺吡喃，二(二茂铁乙炔)乙烷及其三芳胺衍生物通过光致异构化改变末端氧化还原部分之间的电子通讯，以及二茂铁偶氮苯自组装单分子膜，通过结合二茂铁部分的氧化还原反应，在单一绿色光源下进行偶氮苯部分的可逆异构化。对于给体-受体共轭分子，我们发现1-二茂铁乙炔基蒽醌与质子发生环化反应生成吡咯盐，该盐随温度的变化表现为价态互变。我们还发现，1，4-双(二茂铁乙炔)蒽醌在客体分子的吸收作用下发生了可逆的单晶-单晶结构变化。对于杂金属簇合物，我们通过金属二硫杂环与金属羰基的反应合成了几种新型的簇合物。它们表现出独特的氧化还原和光学性质。

项目成果

期刊论文数量（373）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Reversible photochromism of a ferrocenylazobenzene monolayer controllable by a single green light source.

DOI：
10.1039/b713107k
发表时间：
2007-11
期刊：
Chemical communications
影响因子：
4.9
作者：
K. Namiki;Aiko Sakamoto;Masaki Murata;S. Kume;H. Nishihara
通讯作者：
K. Namiki;Aiko Sakamoto;Masaki Murata;S. Kume;H. Nishihara

Redox-assisted ring closing reaction of the photogenerated cyclophanediene form of bis(ferrocenyl)dimethyldihydropyrene with interferrocene electronic communication switching.

DOI：
10.1021/ja8016494
发表时间：
2008-05
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Satoshi Muratsugu;S. Kume;H. Nishihara
通讯作者：
Satoshi Muratsugu;S. Kume;H. Nishihara

Synthesis of heterometal cluster complexes by the reaction of cobaltadichalcogenolato complexes with groups 6 and 8 metal carbonyls.

DOI：
10.1021/ic0513282
发表时间：
2006-01
期刊：
Inorganic chemistry
影响因子：
4.6
作者：
Masaki Murata;S. Habe;S. Araki;K. Namiki;Teppei Yamada;Norikiyo Nakagawa;T. Nankawa;M. Nihei;J. Mizutani;M. Kurihara;H. Nishihara
通讯作者：
Masaki Murata;S. Habe;S. Araki;K. Namiki;Teppei Yamada;Norikiyo Nakagawa;T. Nankawa;M. Nihei;J. Mizutani;M. Kurihara;H. Nishihara

微生物の光合成機能を利用した太陽エネルギー利用技術

利用微生物光合功能的太阳能利用技术