Synthesis of Hierarchical Materials with a Tunable Photoisomerization Response

非技术总结：在该项目中，由材料研究部固态和材料化学项目支持，首席研究员（PI） Natalia Shustova教授和她在南卡罗来纳大学哥伦比亚分校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（如光或热）进行调制。他们还研究了对这些材料的基本理解，阐明了在光照射下裁剪材料特性的概念。这反过来又推动了从自适应透镜和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的材料装配和设计卓越（MADE in SC）协同。除了变革性研究，PI Shustova还继续发展卡罗莱纳女性科学（Wi-Sci）支持网络。Wi-Sci的主要目标是创建和发展一个支持卡罗来纳州高等教育机构女性的网络，包括历史上的黑人学院和大学（HBCUs），从而增加女性获得卡罗来纳州STEM学科至少50%职位的机会。拟议中的Wi-Sci计划为STEM学科的女学生提供了教育和研究机会。技术总结：通过材料设计实现对光异构化动力学的控制是一个必须解决的挑战，以推进光电子学或存储和能量存储领域。然而，允许控制光异构化动力学的基本原理（即实现可逆和快速的材料光响应）仍然非常不发达。该项目由材料研究部固态和材料化学项目支持，进一步发展晶体刺激响应混合材料，展示协调固定刺激响应单元的可调和可逆光异构化，作为材料拓扑的函数。研究小组采用两种途径来组装光响应mof: a)由光致变色配体（如二乙烯基配体）和非光致变色配体组合组装mof；b)通过mof连接子侧基进行光异构化。广泛的光物理分析所产生的光响应框架阐明了与电子结构调制有关的结构-性质关系。此外，该项目促进高中、本科生和研究生的教育和研究机会的整合，特别强调STEM学科的女性。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.