CAREER: Control of Intramolecular Long-Range Charge-Transfer Emission

该奖项全部或部分根据2021年美国救援计划法案（公法117-2）资助。在化学部化学结构，动力&学机制B计划的支持下，康涅狄格大学化学系的Tomoyasu Mani正在开发产生和控制分子内长程辐射电荷复合或电荷转移（CT）的策略在凝聚态中发射。表现出有效的分子内长程CT发射的分子有可能：（1）改变现有的工具，如有机发光二极管和生物医学成像探针，（2）导致新的量子技术，利用其对磁场和手性的独特响应。教育活动计划开发实验光化学模块，向高中和低年级本科生介绍化学的基本概念。这些模块将在各种计划中实施，包括为高中生和本科生普通化学实验室举办的国际研讨会，以鼓励这些早期学生考虑在科学，技术，工程和数学（STEM）领域从事职业。 从长程分子内类似物的CT发射的报告是稀缺的，因此，必要的知识，以产生有效的长程CT发射是缺乏的。这个CAREER项目使用一系列定义明确的供体-桥-受体（D-B-A）分子和多种光谱和计算方法来生成一个全面的数据集，用于评估当前理论框架的有效性，从而提供了一个进一步扩展现有形式主义的机会。这项工作旨在解决目前在电子转移，自旋化学和材料设计领域的知识差距，采用CT发射的应用，创造新的进步机会。具体目标是：（1）通过阐明能级和几何结构等关键参数，建立最大化D−B−A系统中长程CT发射的策略;（2）通过外部刺激（如磁场和手性）控制长程CT发射;以及（3）为高中生和低年级本科生开发交互式光化学模块，该奖项反映了NSF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。

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2).WIth support from the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Tomoyasu Mani of the Department of Chemistry at the University of Connecticut is developing strategies for producing and controlling intramolecular long-range radiative charge recombination or charge transfer (CT) emission in a condensed phase. Molecules that exhibit efficient intramolecular long-range CT emission have the potential to: (1) transform existing tools such as organic light-emitting diodes and biomedical imaging probes and (2) lead to new quantum technologies that leverage their unique responses to a magnetic field and chirality. Educational activities are slated to develop experimental photochemistry modules that introduce the basic concepts of chemistry to high school and lower division undergraduate students. The modules will be implemented in various programs, including an international workshop for high school students and undergraduate general chemistry laboratories, to encourage such early stage students to consider pursuing careers in science, technology, engineering, and mathematics (STEM) fields. Reports of CT emission from long-range intramolecular analogs are scarce; therefore, the necessary knowledge to produce efficient long-range CT emission is lacking. This CAREER project uses a series of well-defined donor−bridge−acceptor (D−B−A) molecules and a multitude of spectroscopic and computational methods to generate a comprehensive dataset for assessing the validity of the current theoretical framework, thus providing an opportunity to extend existing formalisms further. This work seeks to address knowledge gaps present in the fields of electron transfer, spin chemistry, and materials design for applications that employ CT emission, creating new opportunities for advancement. The specific objectives are: (1) to establish strategies to maximize long-range CT emission in D−B−A systems by clarifying the key parameters like energy levels and geometry; (2) to control long-range CT emission by external stimuli such as magnetic field and chirality; and (3) to develop interactive photochemistry modules for high school students and lower division undergraduate students, to introduce students to chemistry concepts associated with recent advances in photochemistry and photophysics.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.