Creation of multi-dimensional structures of functional molecules by metal complexation reactions

通过金属络合反应创建功能分子的多维结构

• 批准号: 11309003
• 负责人: NISHIHARA Hiroshi
• 金额: $ 19.69万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11309003/
• 关键词: metal nanoparticles; azo-coningated comolexes; photochromic complexes; donor-acceptor interaction; quinone; ferrocene; redox; intramolecular electron transfer; 錯体; 共役; 高次構造; オリゴマー; フラスター; ポリマー; クラスター

To construct new multi-dimensional functional molecular systems by utilizing complex reactions of transition metal complexes has been investigated in this research project. The molecular systems that have been focused are 1) azo-conjugated metal complexes with photo-functions, 2) donor-acceptor conjugated complexes with an ability of proton-coupled intramolecular electron-transfer reactions, and 3) metal nanoparticles modified with redox- and photo-functional complexes. The summary of the results is as follows.The trans-to-cis isomerization of azoferrocene proceeds not only by the photoexcitation of the π-π^* transition band but also by photoexcitation of the MLCT (d-π^* transition) band. The trans/cis ratio of the azobenzene-attached bipyridine ligands in their cobalt complex is reversibly altered by a combination of photoirradiation with a single UV light source and the reversible redox change between Co(II) and Co(III). A newly synthesized Ni, Pd and Pt tolylazophenylenedithiolato c … More omplexes 2-4 show reversible trans-to-cis photoisomerization, proto-chromism, and novel proton-coupled cis-to-trans isomerization.The protonation to carbonyl groups of the anthraquinone moiety in 1 -ferrocenylethynylanthraquinone causes intramolecular electron transfer leading to a novel structural change into a η^6-fulvene-cumulene Fe(II) complex. A 2:1 donor-acceptor complex, l,5-bis(ferrocenylethynyl)anthraquinone undergoes a two-step proton response, and the doubly protonated species involves a η^6-fulvene-Fe(II) complex-cumulene structure, and a novel spin-separated form of a ferrocenium (Fe(III)) ion and a semiquinone radical in the solution. Furthermore, the complex is in a thermal equilibrium between the valence tautomers of a donor-acceptor system in the solid state.Synthesis and electrochemical deposition behavior of biferrocene and anthraquinone derivative-modified Au and Pd clusters have been investigated. It is also possible to fabricate hetero structures by alternative electrodeposition of Bfc-modified gold and palladium nanoparticles. Less

本课题研究利用过渡金属配合物的络合反应构建新的多维功能分子体系。重点研究的分子体系有：1)具有光功能的偶氮共轭金属配合物；2)具有质子偶联分子内电子转移反应能力的供体-受体共轭配合物；3)氧化还原和光功能配合物修饰的金属纳米颗粒。结果总结如下。偶氮二茂的反式到顺式异构化不仅通过π-π^*跃迁带的光激发进行，而且还通过MLCT （d-π^*跃迁）带的光激发进行。偶氮苯偶联吡啶配体在钴配合物中的反顺比通过单一紫外光源的光照射和Co（II）和Co（III）之间的可逆氧化还原变化可逆地改变。新合成的镍、钯和铂二聚偶氮苯二硫代化合物的配合物2-4表现出可逆的反-顺光异构化、原变色和新型的质子偶联顺-反异构化。在1 -二茂铁乙炔蒽醌中，蒽醌部分的质子化成羰基引起分子内电子转移，从而导致一种新的结构变化，形成η^6-富烯-聚culculene Fe（II）配合物。一个2:1的供体-受体配合物1,5 -双（二茂铁乙炔基）蒽醌经历两步质子反应，双质子化的物质包括η^6-fulvene-Fe（II）配合物-cumulene结构，以及溶液中二茂铁（Fe(III)）离子和半醌自由基的一种新的自旋分离形式。此外，该配合物在固体状态下在供体-受体系统的价互变异构体之间处于热平衡状态。研究了二茂二酚和蒽醌衍生物修饰金、钯簇的合成及其电化学沉积行为。通过电沉积bfc修饰的金和钯纳米粒子也可以制备异质结构。少

项目成果

M.Yamada, A.Kuzume, M.Kurihara, K.Kubo, H.Nishihara: "Formation of a novel porphyrin-gold nanoparticle network film induced by infrared light irradiation"Chemical Commmmunications. 2476-2477 (2001)

M.Yamada、A.Kuzume、M.Kurihara、K.Kubo、H.Nishihara：“红外光照射诱导新型卟啉-金纳米颗粒网络薄膜的形成”化学通讯。

Y.Yamada, J.Mizutani, M.Kurihara, H.Nishihara: "Synthesis of a New Bis(ferrocenyl)ruthenacyclopentatriene Compound with a Significant Inter-metal Electronic Communication"Journal of the Organometallic Chemistry. 637-639. 80-83 (2001)

Y.Yamada、J.Mizutani、M.Kurihara、H.Nishihara：“具有显着金属间电子通讯的新型双（二茂铁基）钌环戊三烯化合物的合成”有机金属化学杂志。

M.Yamada,T.Tadera,K.Kubo,H.Nishihara: "Electroreductive Deposition of Anthraquinone Derivative-Attached Au Clusters : Optical Properties and STM Observation of the Electrodeposited Cluster Film"Langmuir. (印刷中).

M. Yamada、T. Tadera、K. Kubo、H. Nishihara：“蒽醌衍生物附着的金团簇的电还原沉积：电沉积团簇膜的光学特性和 STM 观察”Langmuir（正在出版）。

H.Nishihara, M.Kurashina, K.Aramaki, K.Kubo: "Near-IR Photoconductivity of Poly(1, 1'-dihexylferrocenylene)-TCNE CT Complex"Synth. Metals. 101(1-3). 457-458 (1999)

H.Nishihara、M.Kurashina、K.Aramaki、K.Kubo：“聚(1, 1-二己基二茂铁)-TCNE CT 复合物的近红外光电导性”合成。

T.Horikoshi, M.Itoh, M.Kurihara, K.Kubo, H.Nishihara: "Synthesis, Redox Behaviors and Electrodeposition of Biferrocene-modified Gold Clusters"J. Electroanal. Chem.. 473(1-2). 113-116 (1999)

T.Horikoshi、M.Itoh、M.Kurihara、K.Kubo、H.Nishihara：“联二茂铁修饰金团簇的合成、氧化还原行为和电沉积”J。