CAREER: Molecular Packing of Pi-Conjugated Polymers through Fused Hydrogen Bond-mediated Self-assembly

职业：通过熔融氢键介导的自组装进行 Pi 共轭聚合物的分子堆积

• 批准号: 1554851
• 负责人: Yu Zhu
• 金额: $ 53.87万
• 依托单位: University of Akron
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554851&HistoricalAwards=false
• 关键词: CAREER; Molecular; Packing; Pi; Conjugated

NON-TECHNICAL SUMMARY:Understanding and controlling molecular packing in electrically conducting polymers could lead to the design of high-performance polymers, which is important for applications requiring flexible, light, and economical electronic materials. This CAREER research involves the study of new types of polymers that have fused sites along their molecules enabling hydrogen bonding. Studying the transition from latent to actual hydrogen bonding states will provide the added benefit of direct patterning of conducting polymers, leading potentially to more efficient fabrication of integrated circuits in organic electronics. Results of this research will help to build an understanding of the structural control in organic materials and contribute to the elucidation of structure-property relationships for electrically conductive polymers. The educational and outreach component of this project is to motivate and inspire students about science and technology and encourage their consideration of careers in STEM fields, especially targeting underrepresented groups in the STEM fields, including women and minorities. The basic concepts of this research will be disseminated to broader lay audiences through the partnership with the University of Akron (UA) public relations and the Akron Global Polymer Academy who provide research news to the general public and materials to K-12 teachers nationwide, respectively. The educational efforts will be offered to students at all levels from middle school to graduate school through several programs. The PI will design lectures for local science Olympiad targeting middle school students. Through partnership with local high schools and professional societies, summer internships in the lab will be provided to high school students. The PI will continue engaging in outreach targeting local community colleges. In addition, this award will allow the PI to develop a new special topic lecture for conjugated polymers for the students at U. Akron. TECHNICAL SUMMARY:Control of charge transfer in organic materials essentially requires the control of intermolecular interactions to achieve the desired molecular packing, crystal structure, and alignment/interconnection of the crystalline grains. This CAREER research seeks to study pi-conjugated polymers with fused hydrogen bonding on the polymer main chain. Such an analysis will provide a fundamental framework to control the pi-pi stacking by strong and directional intermolecular hydrogen bonds. Results of this research will help to build an understanding of the structural control in organic materials and contribute to the elucidation of structure-electronic property relationships for conjugated polymers. In this research, a complete list of hydrogen bonded pi-conjugated pigment molecules and oligomers based on graph-set theory will be investigated firstly. Next, their single-crystal structures will be explicitly determined to understand how hydrogen bonding will affect the pi-pi stacking of the molecules. Finally, polymers with latent hydrogen bodning will be synthesized and converted to polymers with fused hydrogen bonding. Their thin-film structure, morphology, and electronic properties will be investigated. The technical objectives of the research include: 1) Establish a knowledge base regarding conjugated pigments and conjugated oligomers with fused hydrogen bonds; 2) Create a basis for the rational design of fused hydrogen bonding in conjugated molecules; 3) Investigate the conjugated polymers with fused hydrogen bonding and quantify and elucidate the role of hydrogen bonding in thin-film structure and electronic properties.

了解和控制导电聚合物中的分子堆积可以设计高性能聚合物，这对于需要灵活，轻便和经济的电子材料的应用非常重要。 这个职业生涯的研究涉及到新型聚合物的研究，有融合的网站沿着他们的分子，使氢键。 研究从潜在到实际氢键状态的转变将提供导电聚合物直接图案化的额外好处，从而可能更有效地制造有机电子中的集成电路。本研究的结果将有助于建立在有机材料的结构控制的理解，并有助于阐明导电聚合物的结构与性能的关系。该项目的教育和外联部分是激励和启发学生了解科学和技术，鼓励他们考虑在STEM领域从事职业，特别是针对STEM领域代表性不足的群体，包括妇女和少数民族。这项研究的基本概念将通过与阿克伦大学（UA）公共关系和阿克伦全球聚合物学院的合作伙伴关系传播给更广泛的非专业观众，他们分别向公众提供研究新闻和全国K-12教师提供材料。教育工作将通过几个项目提供给从中学到研究生院的各级学生。PI将为针对中学生的当地科学奥林匹克竞赛设计讲座。通过与当地高中和专业协会的合作，将为高中生提供实验室的暑期实习机会。PI将继续参与针对当地社区学院的外联活动。此外，该奖项将允许PI开发一个新的专题讲座共轭聚合物的学生在美国。阿克伦控制有机材料中的电荷转移基本上需要控制分子间相互作用以实现所需的分子堆积、晶体结构和晶粒的排列/互连。本CAREER研究旨在研究聚合物主链上具有稠合氢键的π共轭聚合物。这样的分析将提供一个基本的框架，以控制强和定向分子间氢键的π-π堆积。本研究的结果将有助于建立对有机材料中结构控制的理解，并有助于阐明共轭聚合物的结构-电子性质关系。在本研究中，我们将首先研究基于图集理论的氢键π共轭颜料分子和低聚物的完整列表。接下来，将明确确定它们的单晶结构，以了解氢键如何影响分子的π-π堆积。最后，具有潜在氢键的聚合物将被合成并转化为具有稠合氢键的聚合物。将研究它们的薄膜结构、形态和电子性质。本研究的技术目标包括：1）建立关于具有稠合氢键的共轭颜料和共轭低聚物的知识库; 2）为共轭分子中稠合氢键的合理设计创造基础; 3）研究具有稠合氢键的共轭聚合物，量化和阐明氢键在薄膜结构和电子性质中的作用。

项目成果

Hydrogen-Bonding-Mediated Solid-State Self-Assembled Isoepindolidiones (isoEpi) Crystal for Organic Field-Effect Transistor

• DOI: 10.1021/acs.jpcc.7b11992
• 发表时间: 2018-03-22
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Zhang, Haichang;Liu, Kewei;Zhu, Yu
• 通讯作者: Zhu, Yu

Crystalline Organic Pigment-Based Field-Effect Transistors

• DOI: 10.1021/acsami.7b03170
• 发表时间: 2017-07-05
• 期刊: ACS APPLIED MATERIALS & INTERFACES
• 影响因子: 9.5
• 作者: Zhang, Haichang;Deng, Ruonan;Zhu, Yu
• 通讯作者: Zhu, Yu

A Superionic Conductive, Electrochemically Stable Dual-Salt Polymer Electrolyte

• DOI: 10.1016/j.joule.2018.06.008
• 发表时间: 2018-09-19
• 期刊: JOULE
• 影响因子: 39.8
• 作者: Li, Si;Chen, Yu-Ming;Zhu, Yu
• 通讯作者: Zhu, Yu

Investigation of hydrogen-bonding mediated molecular packing of diketopyrrolopyrrole based donor-acceptor oligomers in the solid state

• DOI: 10.1016/j.polymer.2018.11.029
• 发表时间: 2019-01
• 期刊: Polymer
• 影响因子: 4.6
• 作者: Kun Yang;Xiang Li;Yi-Fan Huang;R. Bhatta;Jiawei Liu;M. Tsige;Chien-Lung Wang;Stephen Z. D. Cheng;Yu Zhu