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

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.

分子水平新材料的开发代表了技术的下一个重大进步，超越了驱动当前技术的小型化固态器件。可以在分子水平（即皮米尺度）运行的设备的存储密度比当今最小的集成电路增加了千倍。可以预见，最引人注目的进步将出现在以高选择性监测无数过程的传感器的开发中。实现这些目标需要许多人的技能，但必须包括化学家的重大贡献，他们既能产生新型分子，又能了解颜色、物理特性、电场敏感性、磁态等特性。***我的研究项目通过研究从含有新元素组合的材料中添加和去除电子的能量学和机制，为实现这一目标做出了贡献。本文描述的工作有两个主要焦点：（i）目标物质化学合成的进展和（ii）对添加和/或从中去除电子的后果的详细研究。这些新材料包含不同的成分，通常是“供体”和“受体”。一个项目将根据 V 族元素对一系列供体进行精心设计的修改，将设计的结构与电子转移倾向联系起来。另一项研究将对最近一类使用二价碳的捐助者进行同样的研究。在第三个项目中，此类供体将与来自第三族元素的受体一起进行检查，这些受体已被证明具有加速添加或去除氢气的能力。在这里，电子转移可以探测这些转变的驱动力。我还建议对一类电子离域的 V 族和 VI 族元素化合物作为具有金属受体的供体进行类似的分析，其中电子转移程度无法直接量化。这种“非无辜”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预计能够起到电场依赖性开关的作用，通过施加电势来开启活动。***我使用惰性气氛室进行合成和测量。分子结构最重要的是通过单晶 X 射线衍射方法确定。电气工作采用特殊电路，能够以高度受控的方式改变施加的电压，并高精度测量非常小的电流。电路/化学界面处的物质表征涉及用可见光/紫外光，特别是电子顺磁共振光谱进行探测。执行这项工作所需的所有主要仪器均已到位。