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

基本信息

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

项目摘要

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教授得到了大分子，超分子和纳米化学（MSN）的设计，综合和表征置二烯型分子的设计，合成和表征基于偶氮烯的组合（5-和7会员）的电荷运输能力运输。目的是开发具有与有机电子，计算机，光电和储能（电池）应用相关的功能改善的分子。主要重点是靶向由多个偶氮单元组成的分子，以实现有效的分子电荷转运和整流。这样的分子为创建用于最少功耗的电子设备的电子设备的超小分子组件提供了潜力。该项目提高了我们对通过单分子的电荷传输的理解。它还为开发功能材料的平台提供了由自组装单层修饰的表面。该奖项支持在跨学科研究环境中对研究生和本科生的培训。与克莱顿州立大学（主要是本科机构与非裔美国学生基础的本科机构）的合作伙伴关系吸引了来自代表性不足的少数群体的学生，并参与了该项目。 PI对科学专业的学生和受到慢性疾病影响的教师面临的挑战提出了第一手视角，以追求他们的教育和专业志向。通过展示该项目在专业会议上的科学和人力资源发展成果，以及以社区为中心的正式场所，PI的倡导强调了社会的好处，即通过纳入慢性病的人来增强大学校园的多样性。基于叠氮的平台，表现出氧化还原，电子和光电特性，通常通过使用苯芳香芳烃而无法访问。这些分子设计为具有锚定基团，例如墨托和异基亚诺，能够在表面上进行自组装，而不会影响方位型支架的芳香性。 DFT计算用于为方位生分子的设计提供信息。这些产品的表征和测试是纳米电子设备中的潜在组件。具体目的是：（1）设计不对称锚定的有机接头，这些接头具有关键的结构刚度和桥梁前沿分子轨道的空间分离；（2）评估矿体自组装单层中的电导率/整流曲线和电子传递动力学；（3）构建由至少12电子可逆有机氧化还原能力组成的分子电子储存库，并检查其电荷到定位潜力，包括有机间隔，包括NSF的法定任务和Intfactiac rightia and Intelliatiac and Intelliatiac reigation，这是有机际划分的潜力。