CAREER: Baird's Polycyclic Anti-Aromatic Chromophores & Application to Engineer Crystalline Dyads for Photon Upconversion in the Solid State

在这个职业项目中，由化学部化学结构、动态和机理B计划资助，伊利诺伊理工学院化学系的Anoclase Ayitou教授正在开发用于光子上转换的新型芳香族发色团及其二元衍生物。光子上转换是一种太阳能管理过程，可以帮助最大限度地提高当前光伏设备或太阳能电池的效率。这项研究的最终目标是利用有机光捕获系统的光物理性质来设计下一代有机光子材料。这些材料可以进一步衍生化，不仅设计出高效的光伏器件，还可以设计出用于生物成像的材料。Ayitou教授和他的团队在这个项目中使用了合成有机化学、计算建模、高级光谱学和结晶学的工具，展示了一系列科学技术、教育和推广活动，使科学界和各级学生受益。为此，Ayitou教授为参与本研究的学生提供指导和培训。此外，该项目的教育部分包括在伊利诺伊理工学院和芝加哥南区社区推广STEM教育的外联活动。Baird的抗芳香性是发色团的一个特征，它在基态显示4N-pi电子，在光激发时显示(4n2)-pi的“芳香物种”。本项目旨在了解如何调节多环二亚胺的固有(4n2)-pi芳香性，从而生成具有Baird抗芳香性的新型多环发色团。本项目的另一个方面是基于多环抗芳香族发色团(PAC)的有机二元化合物的合成，可以用来探索能量/光子上转换现象。总体而言，本项目的结果有助于解决以下问题：(1)相对于其分子核心的pi-扩展程度，PAC是否具有更多/更少的抗芳香性？(2)PAC的芳香性扩展是否有助于调节其光物理性质？(3)与天然PAC相比，PAC-二联体在光子上转换方面是否表现出更好的光物理性能？以及(4)来自这些二元体的材料是否可以用作制造光伏和光学设备以及用于生物成像的原料？该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

In this CAREER project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Anoklase Ayitou of the Department of Chemistry at Illinois Institute of Technology is developing novel aromatic chromophores and their dyad derivatives for photon upconversion. Photon upconversion is a solar energy management process that can help maximize the efficiency of current photovoltaic devices or solar cells. The ultimate goal of this research is to exploit the photophysical properties of organic light harvesting systems to devise next generation organic photonic materials. These materials can be further derivatized to engineer not only high-efficiency photovoltaic devices but also materials for biological imaging. Professor Ayitou and his team use the tools of synthetic organic chemistry, computational modeling, advanced spectroscopy and crystallography in this project, which presents a mosaic of scientific techniques, educational and outreach activities that benefit the scientific community and students of all levels. To this end, Professor Ayitou mentors and provides training for students who participate in this research. Additionally, the educational component of the project includes outreach activities that promote STEM education at Illinois Institute of Technology and in the South Side Communities of Chicago. Baird's antiaromaticity is a characteristic of chromophores that showcase 4n-pi electrons in the ground state and (4n+2)-pi "aromatic species" upon photoexcitation. This project aims to understand how tuning the intrinsic (4n+2)-pi aromaticity of polycyclic diimides can generate novel polycyclic chromophores that exhibit Baird's antiaromaticity. Another aspect of this project is the synthesis of polycyclic antiaromatic chromophores (PAC) based organic dyads, which can be used to explore energy/photon upconversion phenomenon. Overall, the results from this project help unravel the following questions: (1) can the proposed PAC be more/less antiaromatic with respect to the degree of pi-extension of their molecular core? (2) would aromatic extension of PAC help modulate their photophysical properties? (3) can the PAC-dyads exhibit superior photophysical properties in comparison with native PAC in photon upconversion? and (4) can materials from these dyads be used as ingredients for photovoltaic and optical devices fabrication and for biological imaging?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.