Research on Combinatorial Functions of Integrated Organic Redox Systems and their Applications for Unimolecular Memory

本项目计划在氧化还原活性分子集成的基础上，开发新的有机响应分子的设计理念。需要解决的主要问题如下：(1)具有电化学双稳定性和表面改性性能的氧化还原响应系统；(2)熔融聚醚结构的合成新策略；(3)在外界刺激下具有相变特性的氧化还原活性分子。我们已经成功地制备了满足第一个主题要求的氧化还原系统，其中一些系统进一步被赋予了多输入多输出功能。选择二硫化物单元或乙基分别作为Au和Si的表面结合连接体。SAM的制备和实现单分子记忆的研究正在进行中。在一些海洋天然产物中发现的融合聚醚骨架应该是研究弱C-H- O氢键聚集的合适基序。在第二个主题中，针对各种聚醚骨架，开发了易于通用的收敛策略。根据新开发的基于乙醛和酰基丙烯腈等价物反应的方案，我们可以合成聚醚天然产物（半毒素B）和含有4-5个醚单位的雪卡毒素的大片段。对其中一些进行的x射线分析显示，观察到几个短的C-H- O接触将带状聚醚与堆叠或二聚体结构连接起来。天然聚醚和非天然聚醚都值得研究。二（二乙烯基）芳烃型电子给体在氧化后的可逆寡聚化是第三个主题方面的杰出成就。深颜色的多阳离子低聚物可以作为稳定的盐分离出来，在还原后再生起始的单体供体。通过在芳基上连接长烷基链，这些材料中的一些充当有机凝胶，从而为动态中间相的设计提供了新的概念，其性质可以通过电化学输入来调节。少

This project has been planned to develop new design concepts on the novel organic responding molecules based on the integration of redox active molecules. The major themes to be tackled with are as follows : (1) Redox response systems with electrochemical bistability and surface modifying properties ; (2) New synthetic strategy for the fused- polyether structures ; (3) Redox active molecules with phase transition properties triggered by external stimuli.We have succeeded in preparing redox systems to meet the requirement in the first theme, and some of them are further endowed with multi-input and multi-output fuctionalities. The disuflide unit or ethynyl groups were selected that act as surface-binding linkers for Au an Si, respectively. Preparation of SAM and examination toward the realization of unimolecular memory are now under way.The fused-polyether skeleton found in some marine natural products should be a suitable motif for studying the aggregation by weak C-H--O hydrogen bonds … More . In the second theme, facile and general convergent strategy was developed for a variety of polyether skeleton. Based on the newly developed protocol based on the reaction between an aldehyde and an acylanion equivalent, we could synthesize polyetheral natural product (hemibrevetoxin B) and the large segments of ciguatoxins with 4-5 ether units. X-ray analyses on some of them have revealed that several short C-H--O contacts were observed that connect tape-shaped polyethers tol the stacked or dimeric strucures. Not only natural but also non-natural polyethers are shown worth investigated.Reversible oligomerization of bis(diarylethenyl)arenes-type electron donors upon oxidation is the outstanding achievement in terms of the third theme. Deeply-colored polycation oligomers could be isolated as stable salts that regenerated the starting monomeric donors upon reduction. By attaching long alkyl chains on the aryl groups, some of these materials act as organic gelators, thus giving a new desing concept for the dynamic mesophase, whose properties can be modulated by electrochemical input. Less