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)计划的支持下，设计、合成和表征能够进行电荷传输的基于蔚蓝的分子(5和7元碳环的组合)。其目标是开发与有机电子、计算机、光电子和储能(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由多个偶氮烯单元组成的分子上，以实现有效的分子电荷传输和整流。这种分子提供了创造超小分子元件的潜力，用于功能最小的电力消耗的电子设备。这个项目提高了我们对单分子电荷传输的理解。它还为开发表面由自组装单分子膜修饰的功能材料提供了平台。该奖项支持在跨学科研究环境中对研究生和本科生进行培训。与克莱顿州立大学(Clayton State University)(一所主要是本科生的机构，学生基础主要是非洲裔美国人)的合作吸引了代表人数不足的少数族裔的学生，并让他们参与到这个项目中来。PI带来了对受慢性病影响的理科学生和教职员工在追求他们的教育和职业抱负方面所面临的挑战的第一手视角。通过在专业会议和不那么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的倡导强调了通过纳入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被协同使用来开发基于非苯类、芳香族天青的平台，这些平台表现出氧化还原、电子和光电性质，通常通过使用苯类芳香族是无法获得的。分子被设计成具有锚定基团，如硫醇和异氰基，能够在不影响天青支架芳香性的情况下在表面自组装。密度泛函理论计算被用来指导偶氮烯分子的设计。这些产品作为纳米电子器件中的潜在组件进行了表征和测试。具体目标是：(1)设计不对称锚定的有机连接物，具有关键的结构刚性和桥的前沿分子轨道的空间分离；(2)评估天青烯自组装单分子膜中的电导/整流分布和电子转移动力学；以及(3)构建由至少具有12电子可逆有机氧化还原容量的天青烯基有机金属纳米络合物组成的分子电子储存库，并检测其电荷离域潜力，包括有机价间耦合。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，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.