Development of Energy Conversion Systems by Use of Inorganic/Organic Hybrid LB Films

利用无机/有机混合LB薄膜开发能量转换系统

• 批准号: 14050027
• 负责人: YAMAGISHI Akihiko
• 金额: $ 20.54万
• 依托单位: Ochanomizu University (2006)The University of Tokyo (2002-2005)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14050027/
• 关键词: photomodulation; chiral metal complex; Langmuir-Blodegett; clay sheet; chiral nematic; azo; heterogeneous asymmetric reaction; chiral sensor; 光-電気エネルギー変換; 光機能性液晶; 金属錯体; キラル; キラルセンシング; 高分子ナノシート; 金属ナノ粒子; 方向制御された電子移動; 金属ナノ分子; 層状無機酸化物; ラングミュ

This work attempted to elucidate a photoresponsive interface with novel functions. The following three topics were studied: (1) To develop an electrode modified with a single layer of exfoliated clay sheets; (2) To control the structure of cholesteric liquid crystal phases by use of photoresponsive metal complexes as a chiral dopant; (3) To achieve asymmetric syntheses by use of clay-metal complex as an adsorbent.As for (1), an electrode modified with a LB film of Δ-[Os(phen)_3]^<2+>/clay was able to discriminate enantiomers of 1,1'-binaphthol electrochemically. An electrode modified with a LB film of amphiphilic Pt(II) complex was used to convert photon energy to electric one (collaboration with Prof.M.Kato (Hokkaido University)).As for (2), tris(β-diketonato)Ru(III) complex with azobenzene moiety was synthesized and used as a chiral dopant to induce chiral nematic phases. The cis-trans isomerization of the complex resulted in the reversible change of helical pitch length under the illumination of UV and visible lights.As for (3), the photo-oxidation reaction of sulfide was performed by being adsorbed on an ion-exchange adduct of Δ-[Ru(bpy)_3]^<2+>/clay. This was a rare example of heterogeneous asymmetric reactions.

本工作试图阐明一种具有新颖功能的光响应界面。本论文主要研究了以下三个方面的问题：（1）单层粘土片修饰电极的研制：（2）利用光敏金属配合物作为手性掺杂剂控制双相液晶相的结构;（3）通过使用粘土-金属络合物作为吸附剂实现不对称合成。用Δ-[Os（phen）_3]^<2+>/粘土LB膜修饰的电极能电化学区分1，1 '-联萘的对映体。用两亲性Pt（II）配合物的LB膜修饰的电极用于将光子能量转换为电能（与M.Kato教授（北海道大学）合作）。对于（2），合成了具有偶氮苯部分的三（β-二酮基）Ru（III）配合物并用作手性掺杂剂以诱导手性双相。在紫外光和可见光照射下，配合物的顺反异构化导致了螺距长度的可逆变化，而化合物（3）的硫化物的光氧化反应是通过吸附在Δ-[Ru（bpy）_3]^<2+>/粘土的离子交换加合物上进行的。这是一个罕见的多相不对称反应的例子。

项目成果

無機ナノシートの化学と応用 分担:粘土コロイドとLB膜

无机纳米片的化学和应用：粘土胶体和LB膜

• 发表时间: 2005
• 作者: 山岸晧彦

Masaya Mitsuishi, Shinji Kikuchi, Tokuji Miyashita, Yutaka Amao: "Characterization of an ultrathin polymer optode and its application to temperature sensors based luminescent europium complexes"J.Mater.Chem.,. 13. 2875-2879 (2003)

Masaya Mitsuishi、Shinji Kikuchi、Tokuji Miyashita、Yutaka Amao：“超薄聚合物光极的表征及其在基于发光铕配合物的温度传感器中的应用”J.Mater.Chem.,。

A Spectroscopic Evidence for Pt-Pt Interaction in a Langmuir-Blodgett Film of an Amphiphilic Platinum(II) Complex

两亲性铂 (II) 配合物的 Langmuir-Blodgett 薄膜中 Pt-Pt 相互作用的光谱证据

• 发表时间: 2004
• 期刊: The Journal of Physical Chemistry B 108
• 作者: Kentaro Kobayashi

Photomodulation of a chiral nematic liquid crystal by the use of a photoresponsive ruthenium(III) complex

• DOI: 10.1021/cm060282n
• 发表时间: 2006-06
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: T. Mitsuoka;Hisako Sato;J. Yoshida;‡§ and Akihiko Yamagishi;Y. Einaga

Parity in the helical twisting power of Ru(II) 1,3-diketonate for C_2 symmetry in a nematic liquid crystal

向列液晶中 C_2 对称性 Ru(II) 1,3-二酮的螺旋扭转力的宇称性

• 发表时间: 2005
• 期刊: J.Am.Chem.So 127
• 作者: J.Yoshida;H.Sato;A.Yamagishi;N.Hoshino
• 通讯作者: N.Hoshino