New Organometallic Radical-Cation Based Homogeneous and Heterogeneous Reactions and Materials

美国国家科学基金0808909摘要：佛蒙特大学，William Geiger (PI)，由美国国家科学基金分析与表面科学项目资助。知识概要：电化学是实践化学家最通用的工具之一。两个最重要的应用领域是分析和催化。其中第一个涉及分子的识别和定量，对于解决环境、生物和医学问题的广泛需求至关重要。拟议的工作旨在开发一种新的分析“传感器”系列，该系列基于用“标记物”标记分析目标的想法，该“标记物”可以通过相当于电气开关的方式打开和关闭。新的标记物来源于一种易于制备的锰配合物，该配合物可以在佛蒙特大学（UVM）先前开发的电解质介质中可逆切换。另一个主要的研究领域是开发低能耗和更环保的方法来利用简单的烯烃，它是一种基于石油的有机构建块，用于制备合成化学家普遍使用的理想有机化合物。一种高效的电化学方法将被开发和评估，其目标是用一种能够电催化所需反应的有机金属铼配合物取代浪费能量的热化学和光化学方法。更广泛的影响：就研究结果而言，拟议工作的成功结果有望扩大有机金属电化学作为化学家和生物化学家解决问题的方法的影响。同样重要的是，化学家们要问，他们的努力如何有助于提高这个国家和我们世界的能源使用效率这一艰巨的任务。只有四种重要的一般能源可供我们使用：核能、热、光和电。我们的目标一直是，并将继续是，培养电化学家在这四个领域中的最后一个领域取得进展。在UVM接受电化学培训的研究生受雇于各种学术，工业和政府研究职位。由于将这些机会扩大到代表性不足的群体是很重要的，因此该项目将通过project Seed（由美国化学学会监督）为经济困难的高中生提供暑期培训项目，并启动一个试点项目，为UVM的代表性不足的本科生提供暑期研究机会，这些本科生来自一所拥有大量少数民族招生的城市大学。由于他们在一个由高度积极的研究生和博士后组成的研究小组中的经历，高中生和访问本科生将更加意识到他们在预科和研究生高等教育中的机会，从而增加他们成为科学专业人员的可能性。

Abstract of NSF 0808909: University of Vermont, William Geiger (PI), supported by the Analytical and Surface Science Program of the National Science FoundationIntellectual Summary: Electrochemistry is one of the most versatile tools available to the practicing chemist. Two of the most important areas of applications are in analysis and catalysis. The first of these deals with the identification and quantification of molecules and is critically important to a wide range of needs addressing environmental, biological, and medical problems. The proposed work seeks to develop a new family of analytical 'sensors' based on the idea of labeling the analytical target with a 'marker' that can be turned on and off by the equivalent of an electrical switch. The new marker is derived from an easily prepared manganese complex which can be reversibly switched in an electrolyte medium previously developed at the University of Vermont (UVM). The other major area of inquiry is intended to develop lower-energy and greener ways to utilize simple olefins, which are oil-based organic building blocks, in the preparation of desirable organic compounds that will be of general use to synthetic chemists. A highly efficient electrochemical method will be developed and evaluated with the goal of replacing energy-wasting thermal and photochemical methods by an organometallic rhenium complex which is capable of electro-catalyzing the desired reactions. Broader Impact: In terms of the research results, a successful outcome to the proposed work is expected to broaden the impact of organometallic electrochemistry as a problem-solving method among chemists and biochemists. It is also important for chemists to ask how their efforts might contribute to the daunting task of increasing the efficiency of energy usage in this country and in our world. There are only four important general energy sources at our disposal: nuclear, heat, light, and electricity. Our goal has been, and continues to be, the training of electrochemists to develop advances in the last of these four areas. Graduate students trained in electrochemistry at UVM are employed in a variety of academic, industrial, and government research positions. Because it is important to expand these opportunities to underrepresented groups, this project will offer summer training projects to financially disadvantaged high school students through Project Seed (overseen by the American Chemical Society) and initiate a pilot project which offers a summer research opportunity at UVM to underrepresented undergraduate students from a city-based college having a large minority enrollment. Thanks to their experience in a research group composed of highly-motivated graduate students and postdocs, the high school and visiting undergraduate students will be more aware of their opportunities in pre- and post-graduate higher education, thereby increasing the probability that they will become scientific professionals.