CAS: Inhibiting Molecular Reorganization via Strategic Surface Binding

在化学系化学结构、动力学和机理-B计划的支持下，佛罗里达州立大学化学和生物化学系的Kenneth Hanson教授试图通过战略表面结合的方式来理解和控制分子扭曲。分子会因受到光、热、磁场等外界刺激而固有地改变其结构(即扭曲)。这些扭曲会对其性质和用途产生破坏性的影响。这项研究的目标是使用光学测量来了解表面结合在决定分子性质方面的作用，并最终使用这一知识来控制分子的反应性、发射强度和稳定性，以便随后用于更有效的催化、照明、太阳能转换等。作为对这些研究工作的补充，该提案引入了“询问科学家游戏”作为直播科学推广活动。每隔一周，汉森教授都会邀请一位不同的博士科学家与社区交流并回答问题。该流是免费的，所有教育水平、社会经济背景和身份的个人都可以使用。分子经历结构变化，以最大限度地减少由外部刺激(如压力、氧化剂/还原剂、磁场或光)产生的高能态的能量。这一过程是所有分子所固有的，但结构上的巨大变化，特别是过渡金属配合物的结构变化，可能会对它们的性质以及随后在催化、照明、太阳能转换等方面的应用产生不利影响。这个项目的中心假设是，战略性的表面结合(即，将多个独立的配体协调到一个表面)抑制了刺激包括的重组，导致激发态寿命延长、电化学可逆性和高能物种的几何“捕获”。为此，这项工作的主要目标是1)合成一系列表面结合基序具有系统变化的铜(I)配位络合物，2)使用光谱和电化学技术来确定表面结合对分子对刺激的响应的影响，3)几何捕获配位不饱和和活性的铜(I)光解产物。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, Professor Kenneth Hanson of the Department of Chemistry and Biochemistry at Florida State University seeks to understand and control molecular distortions by way of strategic surface binding. Molecules inherently change their structure (i.e., distort) in response to external stimuli such as light, heat, magnetic fields, etc. These distortions can have a debilitating impact on their properties and utility. The goal of this research is to use optical measurements to understand the role of surface binding in dictating molecular properties and ultimately use that knowledge to control reactivity, emission intensity, and stability of the molecular for subsequent use in more efficient catalysis, lighting, solar energy conversion, and more. Complementing these research efforts, this proposal introduces "Ask a Scientist Gaming" as a live streaming science outreach endeavor. Every other week, Professor Hanson hosts a different Ph.D. scientist to interface with the community and answer questions. The stream is free and available to individuals of all educational levels, socio-economic backgrounds, and identities. Molecules undergo a structural change to minimize the energy of the high-energy state generated via external stimuli such as pressure, oxidants/reductants, magnetic fields, or light. This process is intrinsic to all molecules but large changes in structure, especially those of transition metal coordination complexes, can have a debilitating impact on their properties and subsequent use in catalysis, lighting, solar energy conversion, and more. The central hypothesis for this project is that strategic surface binding (i.e., coordinating multiple, independent ligands to a surface) inhibits stimuli-included reorganization, resulting in increased excited state lifetimes, electrochemical reversibility, and geometric “trapping” of high energy species. Toward this end, the major goals of this work are to 1) synthesize a series of Cu(I) coordination complexes with systematic variation in the surface binding motif, 2) use spectroscopic and electrochemical techniques to determine the impact of surface binding on the molecules response to a stimulus, 3) geometrically trap coordinatively unsaturated and reactive Cu(I) photolysis products.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.