CAREER: Conformational Control of pi-Conjugated Polymeric Materials through Dynamic Bonds.

职业：通过动态键对π共轭高分子材料进行构象控制。

• 批准号: 1654029
• 负责人: Lei Fang
• 金额: $ 55.98万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-06-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1654029&HistoricalAwards=false
• 关键词: CAREER; Conformational; Control; pi; Conjugated

NON-TECHNICAL SUMMARYThis project aims to investigate the fundamental correlation between the geometry of electrically semiconducting polymer molecules and their corresponding materials properties. Most polymeric molecules possess structural flexibility at the nanometer and subnanometer scales, which leads to various 3D shapes that they can adopt. Such geometric variability impacts a wide range of polymer properties that are important for their applications, especially those related to electronic and optical properties. Precision control of the molecular shapes of semiconducting polymers, however, has been a long-standing scientific challenge. This CAREER project tackles this problem by synthesizing molecules with reversible and controllable interactions between different segments along the polymer chain. Through this approach, planarized geometries of these polymer molecules can be enforced and disrupted on demand, leading to tailored properties as a result of the switchable molecular shapes. Establishment of this structural control may not only enable the access of improved functional performance, but also allow for feasible processing of polymer materials into application-relevant forms. In addition, the knowledge gained in this project will advance fundamental understanding in materials-related sciences and benefit multiple research disciplines and STEM education. The educational component of this program focuses on connecting scientific concepts and real-world personal knowledge for the students through relevant experiments in the lab and immersive learning experiences. The societal impacts of this project include benefits from scientific publications, new course components, educational software, and trained STEM students for academia and industry.TECHNICAL SUMMARYThis program integrates research, education, and outreach activities under the overarching theme of functional polymer materials. Through a synergistic approach combining chemical synthesis, process engineering, and materials characterization, the research project seeks to establish clear fundamental correlations between controlled torsional conformation and materials properties of pi-conjugated systems. This plan is driven by the underlining hypothesis that active control over torsional conformation can significantly impact polymer properties and processability. The key strategy to achieve this objective is the incorporation of controllable intramolecular dynamic bonds into polymer backbones. A systematic design principle to the synthesis and process engineering of such polymers will be developed on the basis of theoretical simulations and experimental feedback. Structure-property relationships of these materials will be investigated through iterative design-test-feedback-optimization cycles. The ultimate goal is to draw a clear structure-property correlation and to establish design principles for tailoring the integrated properties of conjugated polymeric materials. In parallel, educational and outreach activities are planned to enhance chemistry and broad STEM learning outcome synergistically with the research program. The pedagogical focus is to make the essential connections between scientific knowledge and real-life experiences for the next generation of STEM students through an integrated plan combining course development, undergraduate research programs and outreach activities.

非技术摘要该项目旨在研究半导体聚合物分子的几何形状与其相应的材料性能之间的基本相关性。 大多数聚合物分子都具有纳米和亚纳米尺度的结构灵活性，这导致它们可以采用各种 3D 形状。这种几何变化会影响对其应用很重要的多种聚合物性能，特别是与电子和光学性能相关的性能。然而，精确控制半导体聚合物的分子形状一直是一个长期存在的科学挑战。这个职业项目通过合成沿着聚合物链的不同片段之间具有可逆且可控相互作用的分子来解决这个问题。通过这种方法，可以根据需要强制和破坏这些聚合物分子的平面化几何形状，从而通过可切换的分子形状获得定制的特性。这种结构控制的建立不仅可以提高功能性能，还可以将聚合物材料加工成与应用相关的形式。此外，在该项目中获得的知识将增进对材料相关科学的基本理解，并有益于多个研究学科和 STEM 教育。该计划的教育部分侧重于通过实验室中的相关实验和沉浸式学习体验，将科学概念与现实世界的个人知识联系起来。该项目的社会影响包括科学出版物、新课程组件、教育软件以及为学术界和工业界训练有素的 STEM 学生带来的好处。技术摘要该计划在功能性聚合物材料的总体主题下整合了研究、教育和推广活动。通过化学合成、工艺工程和材料表征相结合的协同方法，该研究项目力求在π共轭系统的受控扭转构象和材料特性之间建立明确的基本相关性。该计划是由一个重要的假设驱动的，即主动控制扭转构象可以显着影响聚合物的性能和可加工性。 实现这一目标的关键策略是将可控的分子内动态键结合到聚合物主链中。将在理论模拟和实验反馈的基础上开发此类聚合物的合成和工艺工程的系统设计原理。这些材料的结构-性能关系将通过迭代设计-测试-反馈-优化循环进行研究。最终目标是得出清晰的结构-性能相关性，并建立定制共轭聚合物材料综合性能的设计原则。与此同时，计划开展教育和外展活动，以与研究计划协同提高化学和广泛的 STEM 学习成果。教学重点是通过结合课程开发、本科生研究项目和推广活动的综合计划，为下一代 STEM 学生建立科学知识和现实生活体验之间的重要联系。

项目成果

Palladium bis-pincer complexes with controlled rigidity and inter-metal distance

具有受控刚性和金属间距离的钯双钳配合物

• DOI: 10.1039/d0qi01111h
• 发表时间: 2020
• 期刊: Inorganic Chemistry Frontiers
• 影响因子: 7
• 作者: Yu, Cheng-Han;Zhu, Congzhi;Ji, Xiaozhou;Hu, Wei;Xie, Haomiao;Bhuvanesh, Nattamai;Fang, Lei;Ozerov, Oleg V.
• 通讯作者: Ozerov, Oleg V.

Electron-Deficient Polycyclic π-System Fused with Multiple B←N Coordinate Bonds

• DOI: 10.1021/acs.joc.0c02052
• 发表时间: 2021-01-07
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Cao, Yirui;Zhu, Congzhi;Fang, Lei
• 通讯作者: Fang, Lei

Synthesis and Solution Processing of a Rigid Polymer Enabled by Active Manipulation of Intramolecular Hydrogen Bonds

通过分子内氢键的主动调控实现刚性聚合物的合成和溶液加工

• DOI: 10.1021/acsmacrolett.8b00388
• 发表时间: 2018
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Zhu, Congzhi;Mu, Anthony U.;Wang, Chenxu;Ji, Xiaozhou;Fang, Lei
• 通讯作者: Fang, Lei

Desymmetrized Leaning Pillar[6]arene

去对称斜柱[6]芳烃

• DOI: 10.1002/anie.201805980
• 发表时间: 2018-07-26
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Wu, Jia-Rui;Mu, Anthony U.;Yang, Ying-Wei
• 通讯作者: Yang, Ying-Wei

Extraordinary Redox Activities in Ladder-Type Conjugated Molecules Enabled by B ← N Coordination-Promoted Delocalization and Hyperconjugation

B-N 配位促进的离域和超共轭使梯型共轭分子具有非凡的氧化还原活性

• DOI: 10.1021/jacs.8b11337
• 发表时间: 2018
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zhu, Congzhi;Ji, Xiaozhou;You, Di;Chen, Teresa L.;Mu, Anthony U.;Barker, Kayla P.;Klivansky, Liana M.;Liu, Yi;Fang, Lei
• 通讯作者: Fang, Lei