Redox Active Compounds & Non-innocent Ligands: Synthesis, Structure, Electrochemistry, EPR Spectroelectrochemistry

氧化还原活性化合物

• 批准号: RGPIN-2015-05737
• 负责人: Boeré, René
• 金额: $ 2.55万
• 依托单位: University of Lethbridge
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=685897
• 关键词: Redox; Active; Compounds; Non; innocent; Redox; Active; Compounds; Non; innocent

The development of new materials at the molecular level represents the next great advance in technology beyond the miniaturized solid-state devices that drive current technology. Devices that could operate at the molecular level (that is, on the picometer scale) offer a thousand-fold increase in storage density over the smallest integrated circuits available today. The most spectacular advances can be expected in development of sensors that monitor a myriad of processes with great selectivity. Achieving these goals will require the skills of many, but must include major contributions by chemists who both produce new kinds of molecules and gain understanding of properties: colour, physical characteristics, electric field susceptibility, magnetic states, etc.***My research program contributes to this goal by studying the energetics and mechanisms of adding and removing electrons from materials that contain new combinations of elements. The work described herein has two major foci: (i) advances in chemical synthesis of targeted species and (ii) detailed investigations of the consequences of adding and/or removing electrons from them. These new materials contain distinct components, typically `donors' and `acceptors'. One project will prepare carefully designed modifications to a series of donors based on a Group V element, relating the designed-in structures to the propensity for electron transfer. Another will examine the same for a more recent class of donors employing divalent carbon. In a third project, such donors will be examined along with acceptors from Group III elements, which have demonstrated ability to accelerate the addition or removal of dihydrogen. Here electron transfer can probe the driving forces for these transformations. I also propose to perform similar analyses on a class of electron-delocalized Group V and VI element compounds as donors with metallic acceptors in which the degree of electron transfer is not directly quantifiable. The electrical response of such `non-innocent' entities is an indicator of their true electronic state. Furthermore, the interaction of these entities with a unique chromium compound is expected to be able to function as an electric-field-dependent switch, turning activity on with the application of an electrical potential.***I employ inert-atmosphere chambers for synthesis and measurement. Molecular structures are determined most importantly by single-crystal X-ray diffraction methods. Electrical work employs special circuitry capable of varying the applied voltage in a highly controlled manner and measuring very small currents with high precision. Characterization of species at the circuit/chemistry interface involves probing with visible/ultraviolet light and especially electron paramagnetic resonance spectroscopy. All the required major instruments to perform this work are in place.

分子水平上新材料的开发代表了超出驱动当前技术的微型固态设备以外的技术的下一个巨大进步。可以在分子水平运行的设备（即，在图表刻度上）可提供比当今最小的集成电路的存储密度增加一千倍。在开发传感器时，可以预期最大的进步，这些传感器以极大的选择性监视无数过程。实现这些目标将需要许多人的技能，但必须包括化学家的重大贡献，这些化学家都产生了新型分子并获得对特性的理解：颜色，物理特征，电场易感性，磁性状态等。本文所述的工作有两个主要焦点：（i）靶向物种的化学合成进展以及（ii）添加和/或从中添加和/或去除电子的后果的详细研究。这些新材料包含不同的组件，通常是“捐赠者”和“受体”。一个项目将根据基于V组元素进行精心设计的修改对一系列捐赠者进行准备，将设计的结构与电子传输的倾向联系起来。另一个将研究使用二价碳的捐赠者类同样的捐助者。在第三个项目中，将与第三组元素的受体一起检查此类捐助者，这些捐助者表明能够加速二氢基因的添加或去除。在这里，电子传输可以探测这些转换的驱动力。我还建议对一类电子偏置的V组和VI元素化合物进行类似的分析，作为具有金属受体的供体，其中电子传递程度无法直接量化。这种“非自然”实体的电响应是其真实电子状态的指标。此外，这些实体与独特的铬化合物的相互作用有望充当电场依赖性开关，并随着电势的应用而打开活动。分子结构是通过单晶X射线衍射方法确定的。电气工作采用能够以高度控制的方式改变施加电压的特殊电路，并以高精度测量非常小的电流。在电路/化学界面上物种的表征涉及使用可见/紫外线光，尤其是电子顺磁共振光谱探测。完成这项工作的所有必需的主要工具都已到位。