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Creation of Multifunctional Photochromic Metal Complexes

多功能光致变色金属配合物的制备

基本信息

批准号：
14204066
负责人：
NISHIHARA Hiroshi
金额：
$ 35.53万
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：
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

This project aims at the creation of new photochromic metal complexes, the investigation of their unique multiple functionalities, and the fabrication of novel types of molecular switches and memories by organizing them at the electrode surfaces. Summary of the results obtained is as follows, 1)Azobenzene-bound tris(bipyridine)cobalt complexes and ferrocenylazobenzenes underwent novel reversible trans-cis isomerization of azobenzene moieties using the combination of photoirradiation with a single light source and redox reaction of a metal complex moiety. 2)Photoluminescence properties of azobenzene-bound terpyridine platinum complexes were turned on and off by the reversible trans-cis isomerization of the azobenzene moiety. 3)A mixture of an azobenzene-attached bipyridine ligand, dmpAB, unsubstituted bipyridine, and Cu ions underwent reversible ligand exchange reactions by redox reaction of Cu(II)/Cu(I), and consequently, trans-cis isomerization of azobenzene moieties using the combina … More tion of photoirradiation with a single light source was achieved. 4)Azo-conjugated dithiolato and catecolato complexes underwent proton-catalized cis-to-trans isomerization. 5)SAMs of azobenzene-bound metal terpyridine complexes and ferrocenylazobenzene derivatives were prepared and their photochemical reactions investigated. 6)A new "molecular photo-electro transducer", working in a cyclic manner totally powered with light irradiation, has been constructed. The UV/blue controlled repetitive motion of azobenzene moieties in 6,6'-bis(4"-tolylazo)-4,4'-bis(4-tert-butylphenyl)-2,2'-bipyridine causes reciprocal Cu(I) translocation between two coordination environments, resulting in pumping of the redox potential of Cu(I). Therefore, UV/blue light information can be successfully transformed into an electrode potential change and positive/negative current response, which is closely related to natural visual transduction both functionally and mechanically. 7)A new platinum complex with both an azo-bound dithiolato ligand and an azobenzene-bound bipyridine ligand exhibits testability reversibly controllable using different energy lights. Less

该项目旨在创造新的光致变色金属络合物，研究其独特的多功能，并通过在电极表面组织它们来制造新型的分子开关和存储器。研究结果总结如下：1)偶氮苯与三(联吡啶)钴配合物和二茂铁偶氮苯的可逆反式异构化反应采用单一光源光照和金属络合物部分氧化还原反应相结合的方法。2)通过偶氮苯部分的可逆反-顺式异构化反应，开启和关闭了偶氮苯基三联吡啶铂配合物的光致发光性能。3)偶氮苯连接的联吡啶配体、dmpAB、未取代联吡啶和铜离子的混合物通过铜(II)/铜(I)的氧化还原反应进行了可逆的配体交换反应，从而利用Combina…实现了偶氮苯部分的反式异构化获得了更多的单一光源的光照度。4)偶氮共轭二硫代醇和儿茶酚配合物发生质子催化顺反异构化反应。5)制备了偶氮苯金属三联吡啶配合物和二茂铁偶氮苯衍生物的自组装膜，并研究了它们的光化学反应。6)研制了一种完全靠光辐射循环工作的“分子光电换能器”。紫外光/蓝光控制偶氮苯部分在6，6‘-bis(4“-tolylazo)-4，4’-bis(4-tert-butylphenyl)-2，2‘-bipyridine中的重复运动，导致铜(I)在两个配位环境之间的相互转移，导致铜(I)的氧化还原电势被泵送。因此，紫外光/蓝光信息可以成功地转化为电极电位变化和正/负电流响应，这在功能上和机械上都与自然视觉传递密切相关。7)含有偶氮二硫醇配体和偶氮苯结合联吡啶配体的铂配合物具有可测性，可用不同的能量光进行可逆控制。较少