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

在分子水平上开发新材料代表了推动当前技术的微型化固态器件之外的下一个重大技术进步。能够在分子水平（即皮米级）上工作的器件，其存储密度比目前最小的集成电路高出上千倍。最引人注目的进步可以预期在传感器的发展，监测无数的过程具有很大的选择性。实现这些目标将需要许多人的技能，但必须包括化学家的主要贡献，他们既能产生新型分子，又能理解性质：颜色，物理特性，电场敏感性，磁性状态等。我的研究计划通过研究从含有新元素组合的材料中添加和移除电子的能量学和机制来实现这一目标。本文所述的工作有两个主要焦点：（i）目标物质的化学合成进展和（ii）添加和/或从中去除电子的后果的详细调查。这些新材料含有不同的成分，通常是"供体"和"受体"。一个项目将准备精心设计的修改一系列捐助者的基础上第五族元素，有关的设计结构的倾向，电子转移。另一个将研究同样的一个更近的一类供体采用二价碳。在第三个项目中，将沿着对这些供体和第三族元素的受体进行研究，这些受体已被证明有能力加速添加或去除二氢。在这里，电子转移可以探测这些转变的驱动力。我还建议进行类似的分析一类的电子离域的第V和VI族元素化合物与金属受体的电子转移的程度是不能直接量化的捐助者。这种"非无辜"实体的电反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性。我使用惰性气氛室进行合成和测量。最重要的是通过单晶X射线衍射方法确定分子结构。电气工作采用特殊的电路，能够以高度可控的方式改变施加的电压，并以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。进行这项工作所需的所有主要仪器都已到位。

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.