New Frontiers in Organic Exciplexes

有机激基复合物的新领域

• 批准号: 2154827
• 负责人: Joseph Dinnocenzo
• 金额: $ 52.5万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154827&HistoricalAwards=false
• 关键词: New; Frontiers; Organic; Exciplexes

With support from the Chemical Structure, Dynamics and Mechanisms-B Program of the Chemistry Division, Professor Joseph Dinnocenzo at the University of Rochester will investigate new classes of excited state intermediates called exciplexes. Exciplexes form when a molecule which has absorbed light forms a complex with another molecule which is still in its ground state. Exciplexes have found use in a wide variety of applications, such as sensors, biological probes, and in organic light emitting diodes (OLED). Due to their greater solubility in water, the new exciplexes formed from charged electron acceptors and/or donors have much greater potential to find use in biological imaging applications than conventional exciplexes. The fundamental knowledge generated by the proposed research could be used to rationally guide the use of the new exciplexes in these and other applications. Research in this project has the potential to generate new foundational knowledge about exciplexes that could contribute to applications in chemistry, biology, and medicine. Based on connections the PI has established at the University of Guam (UoG), a minority institution, the project will engage undergraduates from the UoG, who are underrepresented in STEM (science, technology, engineering and mathematics) in summer research opportunities.Research into emissive exciplexes with different charge types (cationic, anionic, and nonionic) will extend organic exciplexes in new directions, including those that absorb in the visible region of the electromagnetic spectrum to increase their potential utility. Studies to better understand the fundamental photophysical properties of these exciplex intermediates will likely provide insight into the factors that govern their fate (return electron transfer, radiative and nonradiative decay, separation, etc.). This, in turn, would provide valuable knowledge for the design of new exciplexes that have a variety of potential uses, especially for sensing. The discovery of nonionic exciplexes is particularly intriguing because their emission spectra are expected to be largely independent of medium polarity, which would be an unprecedented result for exciplex emissions and one that could be of practical importance. Research objectives for each of the three types of exciplexes include determining which electron acceptor/donor pairs are optimal for emission, the electronic nature of the exciplexes (e.g. electronic coupling matrix elements) through theoretical fitting of the radiative lifetimes of the exciplexes (determined by Time-Correlated Single Photon Counting, TCSPC) and their fluorescence spectra, measuring some of their photophysical properties (e.g. lifetimes and emission quantum yields), examining the exciplex emissions in a variety of media, and using the combined insights from these studies to synthesize intramolecular examples, which have the greatest potential for practical applications.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.

在化学系化学结构，动力学和机制-B计划的支持下，罗切斯特大学的约瑟夫·迪诺森佐教授将研究一类新的激发态中间体，称为激基复合物。当一个吸收了光的分子与另一个仍处于基态的分子形成复合物时，就形成了激基复合物。 已发现激基复合物可用于多种应用，例如传感器、生物探针和有机发光二极管（OLED）。由于它们在水中的更大溶解度，由带电电子受体和/或供体形成的新的激基复合物具有比常规激基复合物大得多的用于生物成像应用的潜力。由拟议的研究产生的基础知识可以用来合理地指导新激基复合物在这些和其他应用中的使用。该项目的研究有可能产生关于激基复合物的新的基础知识，这些知识可能有助于化学，生物学和医学的应用。基于PI在关岛大学（UoG）（一所少数民族院校）建立的联系，该项目将吸引来自UoG的本科生，他们在STEM中的代表性不足（科学、技术、工程和数学）暑期研究机会。研究不同电荷类型的发射激基复合物（阳离子型、阴离子型和非离子型）的应用将在新的方向上扩展有机激基复合物，包括在电磁光谱的可见光区域中吸收的那些，以增加它们的潜在效用。为了更好地理解这些激基复合物中间体的基本物理性质的研究可能会提供对决定其命运的因素（返回电子转移，辐射和非辐射衰变，分离等）的深入了解。反过来，这将为设计具有各种潜在用途的新激基复合物提供有价值的知识，特别是用于传感。非离子激基复合物的发现特别有趣，因为它们的发射光谱预计在很大程度上与介质极性无关，这将是激基复合物发射的前所未有的结果，并且可能具有实际重要性。对于三种类型的激基复合物中的每一种的研究目标包括确定哪种电子受体/供体对对于发射是最佳的，激基复合物的电子性质，（例如电子耦合矩阵元）通过激基复合物的辐射寿命的理论拟合（通过时间相关单光子计数，TCSPC测定）和它们的荧光光谱，测量它们的一些物理性质（例如寿命和发射量子产率），检查各种介质中的激基复合物发射，并使用来自这些研究的组合见解来合成分子内实例，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。