Synthesis of Hierarchical Materials with a Tunable Photoisomerization Response

具有可调光异构化响应的多级材料的合成

• 批准号: 2103722
• 负责人: Natalia Shustova
• 金额: $ 45.89万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2103722&HistoricalAwards=false
• 关键词: Synthesis; Hierarchical; Materials; Tunable; Photoisomerization

Non-technical Summary:With this project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, principal investigator (PI) Prof. Natalia Shustova and her research group at the University of South Carolina at Columbia develop crystalline metal-organic framework (MOF) materials for which electronic properties can be modulated through external stimuli, such as light or heat. They also study the fundamental understanding of these materials which elucidates the concept of tailoring material properties upon light irradiation. This in turn advances applications ranging from adaptive lenses and memory storage devices to nonlinear optics, fuel cells, or field-effect transistors. A specific example is that the proposed crystalline photoresponsive materials enable future optoelectronic materials. The research is synergistic with the Materials Assembly and Design Excellence in South Carolina (MADE in SC). In addition to transformative research, PI Shustova also continues the development of the Carolinian Women in Science (Wi-Sci) Supportive Network. The major Wi-Sci goal is to create and grow a network of support for women currently at the Carolinian institutions of higher education, including historically black colleges and universities (HBCUs), and therefore increase opportunities for women to attain at least 50% of the positions projected for STEM disciplines in the Carolinas. The proposed Wi-Sci initiative integrates educational and research opportunities for female students in STEM disciplines. Technical Summary:Achieving control over photoisomerization kinetics through material design is a challenge that must be addressed to advance the fields of optoelectronics or memory and energy storage. However, fundamental principles, that allow for enabling control over photoisomerization kinetics (i.e., achieve reversible and fast material photoresponse) are still vastly underdeveloped. This project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, furthers the development of crystalline stimuli-responsive hybrid materials exhibiting tunable and reversible photoisomerization of coordinatively-immobilized stimuli-responsive units as a function of material topology. The research team pursues two routes to assemble photoresponsive MOFs: a) assembly of MOFs from a combination of photochromic ligands, such as diarylethene-based ones, and non-photochromic ligands; and b) photoisomerization through MOF-linker side groups. Extensive photophysical analysis of the resulting photoresponsive frameworks are elucidating structure-property relationships related to electronic structure modulation. Additionally, the project promotes integration of educational and research opportunities for high school, undergraduate, and graduate students, with a special emphasis on women in STEM disciplines.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.

非技术摘要：通过该项目，在材料研究部固态和材料化学项目的支持下，南卡罗来纳大学哥伦比亚分校首席研究员 (PI) Natalia Shustova 教授和她的研究小组开发了晶体金属-有机框架（MOF）材料，其电子特性可以通过外部刺激（例如光或热）进行调节。他们还研究了对这些材料的基本理解，阐明了在光照射下调整材料性能的概念。这反过来又推动了从自适应镜头和记忆存储设备到非线性光学、燃料电池或场效应晶体管的应用。一个具体的例子是所提出的晶体光响应材料使未来的光电材料成为可能。该研究与南卡罗来纳州材料组装和卓越设计 (MADE in SC) 具有协同作用。除了变革性研究之外，PI Shustova 还继续发展卡罗莱纳女性科学 (Wi-Sci) 支持网络。 Wi-Sci 的主要目标是为目前在卡罗莱纳州高等教育机构（包括传统黑人学院和大学 (HBCU)）中的女性创建和发展一个支持网络，从而增加女性获得至少 50% 的机会卡罗莱纳州 STEM 学科的职位预计。拟议的 Wi-Sci 计划整合了 STEM 学科中女学生的教育和研究机会。技术摘要：通过材料设计实现对光异构化动力学的控制是推动光电子学或内存和能量存储领域发展必须解决的挑战。然而，允许控制光异构化动力学（即实现可逆且快速的材料光响应）的基本原理仍然远远不发达。该项目得到了材料研究部固态和材料化学项目的支持，进一步开发了晶体刺激响应杂化材料，该材料表现出作为材料拓扑函数的配位固定刺激响应单元的可调和可逆光异构化。研究小组寻求两种组装光响应MOF的途径：a）通过光致变色配体（例如基于二芳基乙烯的配体）和非光致变色配体的组合组装MOF； b) 通过 MOF 连接体侧基进行光异构化。对所得光响应框架的广泛光物理分析正在阐明与电子结构调制相关的结构-性能关系。此外，该项目促进高中生、本科生和研究生的教育和研究机会的整合，特别强调 STEM 学科中的女性。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力评估进行评估，被认为值得支持。优点和更广泛的影响审查标准。

项目成果

Breaking the photoswitch speed limit

突破光电开关速度限制

• DOI: 10.1038/s41467-023-43405-w
• 发表时间: 2023-11-20
• 期刊: Nature Communications
• 影响因子: 16.6
• 作者: Thaggard, Grace C.;Park, Kyoung Chul;Lim, Jaewoong;Kankanamalage, Buddhima K. P. Maldeni;Haimerl, Johanna;Wilson, Gina R.;McBride, Margaret K.;Forrester, Kelly L.;Adelson, Esther R.;Arnold, Virginia S.;Wetthasinghe, Shehani T.;Rassolov, Vitaly A.;Smith, Mark D.;Sosnin, Daniil;Aprahamian, Ivan;Karmakar, Manisha;Bag, Sayan Kumar;Thakur, Arunabha;Zhang, Minjie;Tang, Ben Zhong;Castano, Jorge A.;Chaur, Manuel N.;Lerch, Michael M.;Fischer, Roland A.;Aizenberg, Joanna;Herges, Rainer;Lehn, Jean-Marie;Shustova, Natalia B.
• 通讯作者: Shustova, Natalia B.

Confinement-Driven Photophysics in Hydrazone-based Hierarchical Materials

腙类分层材料中约束驱动的光物理

• 发表时间: 2023-01
• 期刊: Angewandte Chemie Angewandte Chemie international edition in English Supplement
• 作者: Thaggard, G. C.;Leith, G. A.;Sosnin, D.;Martin, C. R.;Park, K. C.;McBride, M. K.;Lim, J.;Yarbrough, B. J.;Maldeni Kankanamalage, B. K.;Wilson, G. R.;et al
• 通讯作者: et al

Stimuli-Modulated Metal Oxidation States in Photochromic MOFs

光致变色 MOF 中的刺激调制金属氧化态

• DOI: 10.1021/jacs.1c11984
• 发表时间: 2022-02
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Martin, C. R.;Park, K. C.;Leith, G. A.;Yu, J.;Mathur, A.;Wilson, G. R.;Gange, G. B.;Barth, E. L.;Ly, R. T.;Manley, O. M.;et al
• 通讯作者: et al

Graphitic supramolecular architectures based on corannulene, fullerene, and beyond

基于球烯、富勒烯等的石墨超分子结构

• DOI: 10.1039/d1cc02896k
• 发表时间: 2021-10
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Leith, Gabrielle A.;Shustova, Natalia B.
• 通讯作者: Shustova, Natalia B.

Traffic Lights for Catalysis: Stimuli‐Responsive Molecular and Extended Catalytic Systems

催化红绿灯：刺激响应分子和扩展催化系统

• DOI: 10.1002/anie.202302859
• 发表时间: 2023-04
• 期刊: Angewandte Chemie International Edition
• 作者: Thaggard, Grace C.;Haimerl, Johanna;Fischer, Roland A.;Park, Kyoung Chul;Shustova, Natalia B.
• 通讯作者: Shustova, Natalia B.