Metal Complexes of Donor-Bridge Acceptor Biradical Ligands: Testing Models for Electron Transfer/Transport/Quantum Interference and Controlling Excited State Wave Functions

在这个由化学部化学结构、动态和机制B项目资助的项目中，北卡罗来纳州立大学化学系的David a . Shultz教授将详细研究分子结构与电子传递方式之间的关系。这项研究的目标是在分子的形状和结构与电子传递之间建立清晰的联系，这对依赖电子传递的材料和设备的设计是有用的。研究结果将应用于下一代的分子电子学、自旋电子学、光子学、有机发光二极管和人工光合反应器。拟议的研究包含分子合成、结构、光谱学、反应性和理论等要素，因此非常适合科学家的综合教育。舒尔茨团队在培养科学家（包括本科生和来自代表性不足群体的科学家）方面拥有丰富的经验，这些科学家将在学术界、政府实验室、工业和企业中从事职业。外展活动包括接待和培训来自当地历史悠久的黑人学院/大学（HBCU） Shaw大学的本科生暑期研究人员。电子供体-受体相互作用在分子水平上控制电子转移和传递。因此，它们在生物和人工电子转移、光合作用、太阳能转换和分子电子学/自旋电子学中是至关重要的基础元素。提出的研究的第一个重点描述了Schultz小组继续努力阐明供体-桥体-受体系统中的电子耦合，其中供体片段是金属-半醌，受体是硝基氮氧化物自由基，两者之间的磁性电子自旋-自旋交换耦合与供体-受体电子耦合的平方成正比。该研究的第二个重点描述了旨在利用光产生的双基激发态中的交换耦合（通过配体到配体的电荷转移）来探测并最终控制激发态过程并模拟激子-极化子相互作用的研究。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor David A. Shultz of the Department of Chemistry at North Carolina State University will develop detailed relationships between a molecule's structure and how it transports electrons. The goal of this research is to develop lucid connections between a molecule's shape and structure and electron transport, which are useful to the design of materials and devices that rely on electron transport. The results will have application in the next generations of molecular electronics and "spintronics" (electron spin-based electronics), photonics, organic light-emitting diodes and artificial photosynthetic reactors. The proposed research contains elements of molecular synthesis, structure, spectroscopy, reactivity and theory, and is thus well suited for an integrated education of scientists. The Shultz group has extensive experience in training scientists (including undergraduates and those from underrepresented groups) who go on to careers in academia, government laboratories, industry and entrepreneurship. Outreach activities involve hosting and training undergraduate summer researchers from Shaw University, a local Historically Black College/University (HBCU). Electron donor-acceptor interactions control electron transfer and transport at the molecular level. They are thus crucial, foundational elements in biological and artificial electron transfer and photosynthesis, solar energy conversion and molecular electronics/spintronics. The first thrust of the proposed research describes continued efforts in the Schultz group toward an elucidation of electronic coupling in Donor-Bridge-Acceptor systems in which the donor fragment is a metal-semiquinone and the acceptor is a nitronylnitroxide radical, and the magnetic electron spin-spin exchange coupling between the two is directly proportional to the square of the Donor-Acceptor electronic coupling. The second thrust of the proposed research describes studies aimed at using exchange coupling in photogenerated biradical excited states (via ligand-to-ligand charge transfer) to probe and ultimately to control excited state processes and to mimic exciton-polaron interactions.