CAS: Near-IR Absorbing Intramolecular Charge Transfer Complexes: Syntheses, Symmetry-Breaking Charge Transfer, and Charge Transfer Reversal by External Stimuli

CAS：近红外吸收分子内电荷转移复合物：合成、对称破坏电荷转移和外部刺激引起的电荷转移逆转

• 批准号: 2000988
• 负责人: Hong Wang
• 金额: $ 40.43万
• 依托单位: University of North Texas
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2000988&HistoricalAwards=false
• 关键词: CAS; Near; IR; Absorbing; Intramolecular

In this project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Francis D’Souza of the Department of Chemistry at the University is developing new classes of charge transfer complexes able to absorb light in the near-infrared region. The research could lead to materials with novel optoelectronic properties, which are needed for efficient solar energy harvesting devices and luminescent sensors. The project lies at the interface of organic, physical and materials chemistry, and is well suited to the education of scientists at the undergraduate and graduate levels. The project provides extensive teaching and training of graduate students, and undergraduate students. The technical knowledge, problem-solving abilities, and communication skills learned through participating in the project help to strengthen the nation’s high technology workforce while contributing to the energy efficiency of clean energy technologies. Outreach efforts contribute to a highly diversified research group and collaboration with the Elm Fork Education Center to enhance general science education are also part of the project. Professor Francis D’Souza’s group will address several scientific challenges. First, can the absorption of the intramolecular charge transfer complexes be extended into the near-infrared region and beyond by utilizing highly interacting strong electron donor and strong electron acceptor pairs? Second, can nanocarbon materials such as fullerene, endohedral fullerene and single-wall carbon nanotubes be used to enhance near-infrared absorption and emission in these intramolecular charge transfer complexes? Third, Are the appended photosensitizers capable of triggering efficient ultrafast charge separation upon photoexcitation, thereby leading to charge-separated states? Are novel photochemical events such as symmetry-breaking charge transfer observed in the multi-modular symmetric intramolecular charge transfer complexes? Finally, can external stimulus be used to modulate ground and excited state charge transfer in these intramolecular charge transfer complexes?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.

在该项目中，由化学系化学结构、动态和机理B计划资助，该大学化学系的Francis D‘Souza教授正在开发能够在近红外区吸收光的新型电荷转移络合物。这项研究可能导致具有新型光电性能的材料，这是高效太阳能收集设备和发光传感器所需的。该项目位于有机化学、物理化学和材料化学的交界处，非常适合本科生和研究生的科学家教育。该项目为研究生和本科生提供广泛的教学和培训。通过参与该项目学到的技术知识、解决问题的能力和沟通技能有助于加强国家的高科技劳动力，同时为清洁能源技术的能效做出贡献。外展工作有助于建立一个高度多样化的研究小组，与榆树叉子教育中心合作加强普通科学教育也是该项目的一部分。弗朗西斯·D‘Souza教授的团队将解决几个科学挑战。首先，利用高相互作用的强电子给体和强电子受体对，分子内电荷转移络合物的吸收能否扩展到近红外区和更远的区域？第二，富勒烯、面内富勒烯和单壁碳纳米管等纳米碳材料能否用来增强这些分子内电荷转移络合物的近红外吸收和发射？第三，添加的光敏剂是否能够在光激发时触发有效的超快电荷分离，从而导致电荷分离状态？在多模块对称性分子内电荷转移络合物中观察到新的光化学事件，如对称性破坏电荷转移吗？最后，外部刺激能否被用来调节这些分子内电荷转移复合体中的基态和激发态电荷转移？这一奖项反映了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。

项目成果

Charge‐Transfer in Panchromatic Porphyrin‐Tetracyanobuta‐1,3‐Diene‐Donor Conjugates: Switching the Role of Porphyrin in the Charge Separation Process

全色卟啉中的电荷转移-四氰基丁-1,3-二烯-供体结合物：切换卟啉在电荷分离过程中的作用

• DOI: 10.1002/chem.202102865
• 发表时间: 2021
• 期刊: Chemistry – A European Journal
• 作者: Sekaran, Bijesh;Dawson, Andrew;Jang, Youngwoo;MohanSingh, Kusum V.;Misra, Rajneesh;D'Souza, Francis
• 通讯作者: D'Souza, Francis

Near‐IR Intramolecular Charge Transfer in Strongly Interacting Diphenothiazene‐TCBD and Diphenothiazene‐DCNQ Push‐Pull Triads

强相互作用联苯并噻嗪 – TCBD 和联苯并噻嗪 – DCNQ 推 – 拉三元组中的近红外分子内电荷转移

• DOI: 10.1002/chem.202200348
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Yadav, Indresh S.;Jang, Youngwoo;Rout, Yogajivan;Thomas, Michael B.;Misra, Rajneesh;D'Souza, Francis
• 通讯作者: D'Souza, Francis

Star-Shaped Triphenylamine–Tetracyanobutadiene–Phenothiazine Push–Pull Systems: Role of Terminal Phenothiazine in Improving Charge Transfer

• DOI: 10.1021/acs.jpcc.2c03495
• 发表时间: 2022-07
• 期刊: The Journal of Physical Chemistry C
• 作者: Indresh Yadav;A. Alsaleh;B. Martin;R. Misra;F. D’Souza

Photoinduced Charge Separation Prompted Intervalence Charge Transfer in a Bis(thienyl)diketopyrrolopyrrole Bridged Donor‐TCBD Push‐Pull System

双（噻吩基）二酮吡咯并吡咯桥桥供体 - TCBD 推 - 拉系统中光致电荷分离促进间隔电荷转移

• DOI: 10.1002/anie.202108293
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Khan, Faizal;Jang, Youngwoo;Patil, Yuvraj;Misra, Rajneesh;D'Souza, Francis
• 通讯作者: D'Souza, Francis