Ultrafast Dynamics Occurring in the Ground States of Transition Metal Ccmplexes

在该项目中，由化学部的化学结构，动力学和机制B计划资助，加州圣地亚哥大学化学和生物化学系的Clifford Kubiak教授正在开发进行快速电子转移（ET）反应的金属络合物的新组装体。 电子转移（ET）是每个电子器件工作的基础。ET研究可以阐明将光有效转化为电子的方法，以及随后可用和可储存的化学能。 这个NSF资助的项目研究了新一代的混合价络合物，以研究分子系统中的电子离域行为。这些发现的后果可以扩展到集成电路，量子计算和人工光合作用的发展。与此同时，Kubiak教授的小组还致力于社区外展和科学教育，让K-12和本科生参与前沿基础科学。混合价三核氧桥簇已被证明是有价值的模型系统，用于开发和理解控制速率，转换位置，和极化的基态电子转移的超快（皮秒）的时间尺度上使用红外光谱和电化学探测这些现象。最近的支持期为未来的研究提供了几个关键目标，包括：（i）将混合价络合物共价连接到电极表面并测量电场对混合价络合物势能面的影响;（ii）将电场驱动的ET研究扩展到驱动对催化重要的化学反应;（iii）研究由手性桥连接的混合价复合物，以了解手性分子与自旋之间的相互作用;以及（iv）高自旋混合-该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this project, funded by the Chemical Structure, Dynamics, and Mechanisms B Program of the Chemistry Division, Professor Clifford Kubiak of the Department of Chemistry and Biochemistry at the University of California San Diego is developing new assemblies of metal complexes that undergo fast electron transfer (ET) reactions. Electron transfer (ET) is the basis of operation of every electronic device. ET research can elucidate methods for efficient conversion of light to electrons and, subsequently, usable and storable chemical energy. This NSF-funded project investigates a new generation of mixed-valent complexes to study the behavior of electronic delocalization in molecular systems. The ramifications of these findings can extend to the development of integrated circuits, quantum computing, and artificial photosynthesis. In tandem with this project, Professor Kubiak’s group is also dedicated to community outreach and science education, engaging and involving K-12 and undergraduate students in cutting edge fundamental science.Mixed-valent trinuclear oxo-bridged clusters have proven to be valuable model systems for the development and understanding of the factors that control the rates, switching location, and polarization of ground state electron transfer on the ultrafast (picosecond) timescale using infrared spectroscopy and electrochemistry to probe these phenomena. The most recent support period informed several key aims for future research, including: (i) covalent attachment of mixed-valent complexes to electrode surfaces and measurement of the influence of electric fields on mixed-valent complexes potential energy surfaces; (ii) extending the study of electric field driven ET towards driving chemical reactions important to catalysis; (iii) the study of mixed-valent complexes joined by chiral bridges to understand interactions between chiral molecules and spin; and (iv) the preparation and study of high-spin mixed-valent iron clusters.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.