Design of oligozulene-based organometallics for probing new paradigms in charge delocalization, transport, and storage at the nanoscopic scale

堪萨斯大学的Mikhail V. Barybin教授在化学系的大分子、超分子和纳米化学（MSN）项目的支持下，设计、合成和表征了具有电荷传输能力的基于azulene的分子（由5元和7元碳环组成）。目标是开发与有机电子，计算机，光电和能量存储（电池）应用相关的具有改进功能的分子。一个主要的重点放在靶向分子由多个azulenic单位，使有效的分子电荷传输和整流。这种分子为电子设备提供了以最小功耗运行的超小分子组件的潜力。这个项目提高了我们对单分子电荷输运的理解。它也为开发具有自组装单层修饰表面的功能材料提供了平台。该奖项支持研究生和本科生在跨学科研究环境中的培训。与克莱顿州立大学（主要是一所本科院校，主要是非裔美国学生）的合作伙伴关系吸引了来自代表性不足的少数民族的学生，并让他们参与到项目中来。该项目为理科生和教师在追求教育和职业抱负的过程中受到慢性疾病的影响所面临的挑战提供了第一手的视角。通过在专业会议和非正式的以社区为中心的场所展示该项目的科学和人力资源开发成果，PI的倡导强调了通过包容慢性病患者来增强大学校园多样性的社会效益。在这个项目中，合成、计算、电化学、光谱和表面化学技术协同应用于开发非苯类、芳香族azulene基平台，该平台具有氧化还原、电子和光电子特性，通常通过使用苯类芳香族无法获得。这些分子被设计成具有锚定基团，如巯基和异氰基，能够在表面上自组装而不影响氮基支架的芳香性。DFT计算被用于通知azulenic分子的设计。该产品作为纳米电子器件的潜在组件进行了表征和测试。具体目标是：(1)设计具有关键结构刚度和桥梁前沿分子轨道空间分离的非对称锚定有机连接体；(2)评价azulene自组装单层的电导率/整流曲线和电子转移动力学；(3)构建具有至少12个电子可逆有机氧化还原能力的氮基有机金属纳米配合物的分子电子储层，并研究其电荷离域电位，包括有机价间偶联。该奖项反映了美国国家科学基金会的法定使命，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。

Professor Mikhail V. Barybin of the University of Kansas is supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry to design, synthesize and characterize azulene-based molecules (combination of 5- and 7-membered carbon rings) that are capable of electric charge transport. The goal is to develop molecules with improved functionality relevant to organic electronic, computer, optoelectronic, and energy storage (battery) applications. A major emphasis is placed on targeting molecules comprised of multiple azulenic units to enable efficient molecular charge transport and rectification. Such molecules offer the potential of creating ultra-small molecular components for electronic devices that function with minimal power consumption. This project improves our understanding of charge transport through single molecules. It also affords a platform for the development of functional materials with surfaces modified by self-assembled monolayers. The award supports training of graduate and undergraduate students in an interdisciplinary research environment. A partnership with Clayton State University (a primarily undergraduate institution with a predominantly African American student base) attracts students from underrepresented minority and involves them in the project. The PI brings a first-hand perspective on challenges faced by science students and faculty affected by a chronic illness in pursuit of their educational and professional aspirations. By showcasing the scientific and human resource development outcomes of the project at professional conferences and less formal community-centered venues, the PI's advocacy highlights societal benefits of enhancing the diversity of university campuses through inclusion of persons with chronic illnesses.In this project, synthetic, computational, electrochemical, spectroscopic and surface chemistry techniques are synergistically employed to develop nonbenzenoid, aromatic azulene-based platform that exhibit redox, electronic, and optoelectronic properties, typically inaccessible through the use of benzenoid aromatics. The molecules are designed to have anchoring groups, such as mercapto and isocyano, capable of self assembly on surfaces without affecting the azulenic scaffold's aromaticity. DFT calculations are used to inform the design of the azulenic molecules. The products are characterized and tested as potential components in nanoelectronic devices. The specific aims are: (1) to design asymmetrically anchored organic linkers that feature key structural rigidity and spatial separation of the bridge's frontier molecular orbitals; (2) to evaluate the conductivity/rectification profiles and the electron transfer dynamics in azulene self-assembled monolayers; and (3) to construct molecular electron reservoirs composed of azulene-based organometallic nanocomplexes with at least 12-electron reversible organic redox capacity, and to examine their charge delocalization potential, including organic intervalence coupling.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.