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

在化学系化学结构、动力学机制B项目资助的这一项目中，大卫A.北卡罗来纳州州立大学化学系的舒尔茨将研究分子结构与电子传输方式之间的详细关系。 这项研究的目标是开发分子的形状和结构与电子传输之间的清晰联系，这对依赖电子传输的材料和器件的设计非常有用。 研究结果将应用于下一代分子电子学和“自旋电子学”（电子自旋电子学）、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，反应性和理论的元素，因此非常适合科学家的综合教育。 舒尔茨小组在培训科学家（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，工业和创业中继续职业生涯。 外联活动包括接待和培训来自Shaw大学的本科生暑期研究人员，Shaw大学是当地一所历史悠久的黑人学院/大学（HBCU）。 电子给体-受体相互作用在分子水平上控制电子转移和传输。 因此，它们是生物和人工电子转移和光合作用、太阳能转换和分子电子学/自旋电子学中至关重要的基础元素。 拟议的研究的第一个推力描述了舒尔茨小组对电子耦合在供体桥受体系统，其中的供体片段是一个金属半醌和受体是一个硝酰基氮氧自由基，和两者之间的磁性电子自旋-自旋交换耦合成正比的供体-受体电子耦合的平方说明持续的努力。 拟议的研究的第二个推力描述了旨在使用交换耦合在光生双自由基激发态（通过配体到配体的电荷转移）探测，并最终控制激发态过程和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.