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

设计基于低聚菊烯的有机金属化合物，用于探索纳米尺度电荷离域、传输和存储的新范例

• 批准号: 1808120
• 负责人: Mikhail Barybin
• 金额: $ 30万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808120&HistoricalAwards=false
• 关键词: Design; oligozulene; based; organometallics; probing

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.

堪萨斯大学的 Mikhail V. Barybin 教授在化学系高分子、超分子和纳米化学 (MSN) 项目的支持下设计、合成和表征甘菊环基分子（5 元和 7 元碳环的组合） ）能够进行电荷传输。 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。 主要重点放在由多个甘菊单元组成的靶向分子上，以实现有效的分子电荷传输和整流。 这些分子提供了为电子设备制造超小分子元件的潜力，这些元件以最小的功耗运行。 该项目提高了我们对单分子电荷传输的理解。 它还为开发具有自组装单层改性表面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（一所以非裔美国学生为主的本科院校）的合作关系吸引了少数族裔的学生，并让他们参与到该项目中。 PI 带来了关于受慢性病影响的理科学生和教师在追求教育和职业抱负时所面临的挑战的第一手视角。 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。协同使用计算、电化学、光谱和表面化学技术来开发基于非苯环、芳香甘菊环的平台，该平台表现出氧化还原、电子和光电特性，而这些特性通常无法通过使用苯型芳烃。 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，而不影响天青支架的芳香性。 DFT 计算用于指导天青分子的设计。 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体，其具有关键的结构刚性和桥前沿分子轨道的空间分离； (2) 评估甘菊环自组装单分子层的电导率/整流曲线和电子转移动力学； (3) 构建由具有至少 12 电子可逆有机氧化还原能力的甘菊基有机金属纳米复合物组成的分子电子库，并检查其电荷离域潜力，包括有机间隔耦合。该奖项反映了 NSF 的法定使命，并被视为值得通过使用基金会的智力优点和更广泛的影响审查标准进行评估来支持。

项目成果

Positional Isomers of Isocyanoazulenes as Axial Ligands Coordinated to Ruthenium(II) Tetraphenylporphyrin: Fine-Tuning Redox and Optical Profiles

• DOI: 10.1021/acs.inorgchem.9b01030
• 发表时间: 2019-07-15
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Fathi-Rasekh, Mahtab;Rohde, Gregory T.;Nemykin, Victor N.
• 通讯作者: Nemykin, Victor N.

Homoleptic complexes of isocyano- and diisocyanobiazulenes with a 12-electron, ligand-based redox capacity

• DOI: 10.1039/d3dt01958f
• 发表时间: 2023-07-31
• 期刊: DALTON TRANSACTIONS
• 影响因子: 4
• 作者: Connelly，Patrick T.;Applegate，Jason C.;Barybin，Mikhail V.
• 通讯作者: Barybin，Mikhail V.