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教授得到化学系大分子、超分子和纳米化学（MSN）项目的支持，设计、合成和表征能够进行电荷传输的基于甘菊环的分子（5元和7元碳环的组合）。 目标是开发具有与有机电子、计算机、光电和储能（电池）应用相关的改进功能的分子。 一个主要的重点放在靶向分子组成的多个azulenic单位，使有效的分子电荷传输和整流。 这种分子提供了为电子设备创建超小分子组件的潜力，这些组件以最小的功耗运行。 这个项目提高了我们对单分子电荷传输的理解。 它也提供了一个平台，为功能材料的发展与表面改性的自组装单分子膜。 该奖项支持在跨学科研究环境中培养研究生和本科生。 与克莱顿州立大学（一所以非裔美国人学生为主的本科院校）建立了伙伴关系，吸引了代表性不足的少数族裔学生，并让他们参与该项目。 PI带来了对科学学生和教师在追求他们的教育和职业抱负的慢性疾病所面临的挑战的第一手观点。 通过在专业会议和非正式的社区中心场所展示该项目的科学和人力资源开发成果，PI的宣传强调了通过纳入慢性病患者来提高大学校园多样性的社会效益。在该项目中，合成，计算，电化学，光谱和表面化学技术协同使用，以开发非苯型，芳族基于甘菊环的平台，其表现出氧化还原、电子和光电性质，通常通过使用苯型芳族化合物无法获得。 这些分子被设计成具有锚定基团，例如巯基和异氰基，能够在表面上自组装而不影响azulenic支架的芳香性。 DFT计算用于通知的甘菊环分子的设计。 该产品的特点和测试作为潜在的组件在纳米电子器件。 具体目标是：（1）设计具有关键结构刚性和桥前线分子轨道空间分离的不对称锚定有机连接体;（2）评估甘菊环自组装单分子膜的电导/整流特性和电子转移动力学;和（3）构建由具有至少12-电子可逆有机氧化还原容量的基于甘菊环的有机金属纳米络合物组成的分子电子库，该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

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.