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

职业生涯：贝尔德的多环反芳香族发色团

• 批准号: 2211296
• 负责人: Anoklase Ayitou
• 金额: $ 64.99万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-02-15 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2211296&HistoricalAwards=false
• 关键词: CAREER; Baird; Polycyclic; Anti; Aromatic

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.

在这个由化学系化学结构、动力学和机理 B 项目资助的职业项目中，伊利诺伊理工学院化学系的 Anoklase 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联体衍生物。 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。这些材料可以进一步衍生，不仅可以设计高效光伏器件，还可以设计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、计算模型、先进光谱学和晶体学等工具，展示了一系列科学技术、教育和外展活动，使科学界和各级学生受益。为此，阿伊头教授为参与这项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区社区推广 STEM 教育的外展活动。贝尔德的反芳香性是发色团的一个特征，在光激发时显示出基态的 4n-pi 电子和 (4n+2)-pi“芳香族物质”。该项目旨在了解如何调节多环二酰亚胺的固有 (4n+2)-pi 芳香性可以生成表现出贝尔德反芳香性的新型多环发色团。该项目的另一个方面是合成基于多环反芳香族发色团（PAC）的有机二元组，可用于探索能量/光子上转换现象。总体而言，该项目的结果有助于解决以下问题：（1）所提出的 PAC 就其分子核心的 pi 延伸程度而言是否可以具有更多/更少的反芳香性？ (2) PAC 的芳香族延伸是否有助于调节其光物理性质？ (3) 与天然 PAC 相比，PAC 双体在光子上转换方面能否表现出更优异的光物理性质？ (4) 来自这些二元体的材料可以用作光伏和光学器件制造以及生物成像的成分吗？该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Synthesis and Photophysics of Phenylene Based Triplet Donor–Acceptor Dyads: ortho vs. para Positional Effect on Intramolecular Triplet Energy Transfer

• DOI: 10.1016/j.jpap.2022.100112
• 发表时间: 2022-02
• 期刊: Journal of Photochemistry and Photobiology
• 作者: Young Ju Yun;Manoj K. Manna;N. Kamatham;Jingbai Li;Shuyang Liu;Francesca Peccati;Barry C. Pemberton;G. Wiederrecht;D. Gosztola;Gonzalo Jiménez‐Osés;A. Rogachev;A. Jean-Luc Ayitou

Triplet-triplet annihilation photon-upconversion in hydrophilic media with biorelevant cholesteryl triplet energy acceptors

• DOI: 10.1016/j.jphotochem.2021.113412
• 发表时间: 2021-09
• 期刊: Journal of Photochemistry and Photobiology A-chemistry
• 影响因子: 4.3
• 作者: Young Ju Yun;Jussi Isokuortti;T. Laaksonen;N. Durandin;A. Ayitou

Triplet photodynamic and up-conversion luminescence in donor–acceptor dyads with slip-stacked vs. co-facial arrangement

滑堆积与共面排列的供体-受体二元体中的三重态光动力和上转换发光

• DOI: 10.1039/d1tc05122a
• 发表时间: 2022
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: Yun, Young Ju;Peccati, Francesca;Wiederrecht, Gary P.;Gosztola, David J.;Diroll, Benjamin T.;Jiménez-Osés, Gonzalo;Ayitou, A. Jean-Luc
• 通讯作者: Ayitou, A. Jean-Luc

Substrate Effects in the Self-Assembling of N,N-Diphenylquinodimethyl Thioamide on Transition Metals

• DOI: 10.1021/acs.jpcc.3c01663
• 发表时间: 2023-07-17
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Wang，Kai;Liu，Dairong;Jiang，Nan
• 通讯作者: Jiang，Nan

Photometric sensing of heavy metal ions using a naphthoquinodimethyl-bis-thioamide dye: Selectivity & photophysics of the metal organic complexes

使用萘醌二甲基双硫代酰胺染料对重金属离子进行光度传感：选择性

• DOI: 10.1016/j.jphotochem.2021.113648
• 发表时间: 2022
• 期刊: Journal of Photochemistry and Photobiology A: Chemistry
• 作者: Maharjan, Samjhana;Yun, Young Ju;Okello, Veronica A.;Wiederrecht, Gary P.;Gosztola, David J.;Ayitou, A. Jean-Luc
• 通讯作者: Ayitou, A. Jean-Luc