Electrochiroptics : Novel Molecular Response System

电手性光学：新型分子响应系统

• 批准号: 13440184
• 负责人: SUZUKI Takanori
• 金额: $ 9.6万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440184/
• 关键词: Molecular Response System; Molecular Device; Electrochromism; Redox System; Circular Dichroism; Chirality; Electron Donor; Functionalized Dye; 酸化還元素; 分子不斉; ビナフチル; ヘリセン; テトラシアノキノジメタン

This research project is intended to construct the novel molecular response systems that transduce the electrochemical input into two kinds of spectral outputs, they are UV-Vis and CD spectra. These materials are named as "electrochiroptical response systems", and considered as promising candidates for use as chiral redox memories. Compared with the extensively studied electrochromic materials giving the UV-Vis spectral change as a sole output, there have been only a few successful examples reported so far. Based on our previous results on the multi-stage redox systems endowed with high electrochemical bistability, we have designed several chiral electron donors that can be reversibly transformed into the stable dicationic species. They exhibited drastic changes in UV-Vis as well as CD spectra during the interconversion. The high amplitude in CD signals is one of the central points to be considered in the molecular design, and we have realized it by exciton coupling of two identical chromophores located at the proper positions in these molecules. We are now planning to fix these molecules on the metal surface by making SAM, so that these molecules can be used as molecular devices.

本研究项目旨在构建新型的分子响应系统，将电化学输入转化为两种光谱输出，即UV-Vis光谱和CD光谱。这些材料被命名为“电手性响应系统”，被认为是很有希望用作手性氧化还原存储器的候选材料。与研究广泛的电致变色材料相比，将紫外可见光谱的变化作为唯一的输出，到目前为止只有几个成功的例子报道。基于我们对具有高电化学双稳性的多级氧化还原体系的研究结果，我们设计了几种可以可逆转化为稳定的阳离子物种的手性电子给体。在相互转化过程中，它们的UV-Vis光谱和CD光谱发生了剧烈的变化。CD信号的高幅度是分子设计中要考虑的中心点之一，我们通过位于分子中适当位置的两个相同发色团的激子耦合来实现这一点。我们现在正计划通过制作SAM将这些分子固定在金属表面，这样这些分子就可以用作分子器件。

项目成果

T.Suzuki, H.Higuchi, M.Ohkita, T.Tsuji: "Dual-Mode Electrochromism Switched by Proton Transfer : Dynamic Redox Properties of Bis(diarylmethylenium)-Type Dyes"Chem.Commun.. 1574-1575 (2001)

T.Suzuki、H.Higuchi、M.Ohkita、T.Tsuji：“通过质子转移切换的双模式电致变色：双（二芳基亚甲基）型染料的动态氧化还原性能”Chem.Commun. 1574-1575 (2001)

T. Suzuki, H. Higuchi, M. Ohkita, T. Tsuji: "Dual-mode Electrochromism Switched by Proton-transfer : Dynamic Redox Properties of Bis(diarylmethylenium)-type Dyes"Chem. Commun.. 1574-1575 (2001)

T. Suzuki、H. Higuchi、M. Ohkita、T. Tsuji：“质子转移切换的双模式电致变色：双（二芳基亚甲基）型染料的动态氧化还原性能”Chem。

J. Nishida, T. Suzuki, M. Ohkita, T. Tsuji: "A Redox Switch Based on Dihydro[5]helicene : Drastic Chiroptical Response Induced by Reversible C-C Bond Making/Breaking upon Electron Transfer"Angew. Chem. Int. Ed.. 40. 3251-3254 (2001)

J. Nishida、T. Suzuki、M. Ohkita、T. Tsuji：“基于二氢[5]螺旋烯的氧化还原开关：电子转移时由可逆 C-C 键形成/断裂引起的剧烈手性光学响应”Angew。

西田純一, 鈴木孝紀, 辻 孝: "ヘキサフェニルエタン型化合物を基軸とした酸化還元型応答系の構築"有機合成化学協会誌. Vol.60. 40-51 (2002)

Junichi Nishida、Takaki Suzuki、Takashi Tsuji：“基于六苯基乙烷型化合物的氧化还原反应系统的构建”有机合成化学学会杂志第 40-51 卷（2002 年）。

T.Suzuki, H.Higuchi, T.Tsuji, J.Nishida, Y.Yamashita, T.Miyashi: "Chemistry of Nanomolecular Systems : Toward the Realization of Molecular Device, Chaptar1 Dynamic Redox Systems : Toward The Realization of Unimolecular Memory"T.Nakamura, T.Matsumoto, H.Ta

T.Suzuki、H.Higuchi、T.Tsuji、J.Nishida、Y.Yamashita、T.Miyashi：“纳米分子系统化学：迈向分子器件的实现，Chaptar1动态氧化还原系统：迈向单分子存储器的实现”T