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

伊利诺伊理工大学化学系Anoklase Ayitou教授在化学结构、动力学与机理B项目资助的CAREER项目中，正在开发用于光子上转换的新型芳香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。本研究的最终目标是利用有机光收集系统的光物理特性来设计下一代有机光子材料。这些材料不仅可以进一步衍生为高效率的光电器件，还可以用于生物成像材料。在这个项目中，Ayitou教授和他的团队使用了合成有机化学、计算建模、先进光谱学和晶体学等工具，展示了科学技术、教育和推广活动的马赛克，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，该项目的教育部分还包括在伊利诺伊理工学院和芝加哥南部社区推广STEM教育的外展活动。Baird的抗芳香性是发色团的一个特征，它在基态下显示4n-pi电子，在光激发下显示(4n+2)-pi“芳香物质”。本项目旨在了解如何调整多环二亚胺的固有(4n+2)-pi芳构性，从而产生具有Baird抗芳构性的新型多环发色团。本项目的另一个方面是合成基于多环反芳香发色团（PAC）的有机二元体，用于探索能量/光子上转换现象。总的来说，本项目的结果有助于解开以下问题：(1)所提出的PAC在其分子核的pi延伸程度方面是否具有更多或更少的反芳香性？(2) PAC的芳香扩展是否有助于调节其光物理性质？(3)在光子上转换方面，PAC-dyads是否表现出优于原生PAC的光物理特性？(4)这些材料是否可以用作光伏和光学器件制造以及生物成像的成分？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。

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.