Electroactive Self-Assembled Monolayers: Putting Surface-Confined Redox Reactions to Work

电活性自组装单层膜：使表面限制的氧化还原反应发挥作用

• 批准号: RGPIN-2019-04883
• 负责人: Badia, Antonella
• 金额: $ 2.62万
• 依托单位: Université de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=714651
• 关键词: Electroactive; Self; Assembled; Monolayers; Putting

The proposed research is aimed at harnessing redox-terminated monomolecular films to electrochemically activate, drive, and modulate physicochemical processes at solid-liquid interfaces in ways that can potentially facilitate the development of macro- to nano-scale electrochemical technologies. Self-assembled monolayers (SAMs) of organothiolates, functionalized with ferrocene, biferrocenylene, electron donor or electron acceptor moieties, chemisorbed to gold surfaces are used as electroactive molecular interfaces. Charge-transfer-induced changes in these redox-active SAMs will be exploited for micromechanical actuation and the formation of two-dimensional ensembles, including solid-supported lipid membranes, films of lyotropic liquid crystal nanomaterials, and nanoparticle arrays. The objective of the former research thrust is to establish how small (angstrom-scale) conformational changes can be electrochemically triggered and harnessed to perform much larger-scale mechanical work, while that of the latter is to demonstrate how the interfacial ion pairs or charge transfer complexes generated by a redox stimulus can be used to create surface-adsorbed assemblies. We specifically seek to establish the roles played by the steric crowding of the redox moieties, number of repeat units in the monolayer backbone, (supra-)molecular organization in the monolayer, intermolecular van der Waals interactions, and the strength of the ion pair or charge transfer interactions on the processes investigated. Charge storage in binary SAMs comprising two ferrocene derivatives with nonoverlapping redox potentials, as well as biferrocenylene-terminated SAMs, whose redox stability is far superior to that of the usual ferrocene-terminated counterparts, will be investigated for the development of electrochemically robust multistate molecular switches. Finally, the effect of localized surface plasmon excitation on the Faradaic electrochemistry and chemical lability of surface-tethered molecules will be explored with the aim of facilitating surface-confined electrochemical reactions and enabling the regiospecific chemical functionalization of nanostructures. The expected outcomes are the development of redox- and light-mediated processes for manipulating molecular events at solid-liquid interfaces and that can be used to engineer functional redox-responsive systems such as electromechanical actuators, electronic memories or electrooptical devices.

拟议的研究旨在利用氧化还原终止的单分子膜以电化学激活，驱动和调节固体界面的物理化学过程，以有可能促进宏至纳米尺度电化学技术的发展。有机胆酸的自组装单层（SAMS），用二代二世，双乙烯基苯基，电子供体或电子受体部分，化学上的金表面用作电活性分子界面。这些氧化还原活性SAM的电荷转移诱导的变化将被利用用于微力机械致动，并形成二维合奏，包括固体支撑的脂质膜，溶裂性液晶液晶纳米材料的膜和纳米粒子阵列。以前的研究推力的目的是建立如何在电化学上触发和利用的小（Angstrom尺度）变化以进行大量的机械工作，而后者的机械工作是如何通过互联网刺激产生的界面离子对或电荷传递复合物来创建表面上的组装组合。我们特别寻求建立氧化还原部分的空间拥挤，单层骨架中的重复单元的数量，单层中（上）分子组织在单层中，分子间的范德华相互作用以及离子对的强度或在所研究过程中的离子对或电荷转移相互作用的强度。二进制SAM中的电荷存储包含两个二茂铁衍生物，具有非重叠的氧化还原电势以及双丙基苯基终止的SAM，其氧化还原稳定性远远超过了通常的二甲基终止终止的对应物的氧化还原稳定性，将被研究以用于用于电化学上稳健多的多种型多种型分子开关的发展。最后，将探索局部表面等离子体激发对法拉达电化学的影响和表面螺旋分子的化学稳定性的影响，以促进表面限制的电化学反应并启用纳米结构的降级化学化学功能。预期的结果是开发氧化还原和光介导的过程，用于操纵固定液体界面上的分子事件，可用于设计功能性氧化还原响应系统，例如机电驱动器，电子记忆或电子电器设备。