CAS: ENFORCING EXCITED STATE REACTIVITY BY ALTERING CHROMOPHORE CHARACTERISTICS

CAS：通过改变发色团特性来增强激发态反应性

• 批准号: 1955524
• 负责人: Jayaraman Sivaguru
• 金额: $ 45万
• 依托单位: Bowling Green State University
• 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 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955524&HistoricalAwards=false
• 关键词: CAS; ENFORCING; EXCITED; STATE; REACTIVITY

With this award, the Chemical Structure, Dynamics and Mechanism-B program in the Division of Chemistry supports the fundamental research of Professor Jayaraman Sivaguru and his students at Bowling Green State University (BGSU) in Ohio. The Sivaguru group harnesses the power of light to create sustainable strategies for carrying out new chemical transformations. They develop new models to understand the fundamental aspects and to control light–induced reactivity. The overarching goal is to build complex molecular structures in an energy efficient and sustainable fashion. This project integrates the research and academic goals of teaching and learning to help students gain experimental and intellectual competence. The broader impacts of the program include research by high school students in northwest Ohio through an outreach program called PICNICS (Parents Involvement with Children, Nurturing Intellectual Curiosity in Science). This program provides summer internships for local high school juniors and seniors. This enables the students to learn first-hand about recent advancements in science, and to gain experience working in a cutting-edge research environment in BGSU’s Center for Photochemical Sciences.The research plan develops strategies for directing excited state reactivity, uncovering new photochemical reactivity, and achieving reaction selectivity by altering the normal characteristics of chromophores. The electronic characteristics of reactive chromophores are modified either by internal substitution or through external additives such as Lewis acids. This work is designed to reveal new photochemical pathways and reactivity that are not observed in conventional systems. The research seeks to understand the delicate balance between reactivity, selectivity, dynamics, and lifetimes of molecular excited state and short-lived intermediates. One goal is to create new paradigms related to photochemical and photophysical events using altered chromophore characteristics. The outcome of the proposed investigations provides a platform to build complex molecules with pre-defined configurations, in an energy efficient and sustainable fashion. The results have a significant impact on basic concepts related to the photosciences and broadly influence the fields of synthesis, materials science, organic optoelectronics, catalysis and environmental science. This research provides opportunities for student training and integration of research in public outreach programs.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.

凭借该奖项，化学系的化学结构、动力学和机理-B 项目支持了俄亥俄州鲍灵格林州立大学 (BGSU) Jayaraman Sivaguru 教授和他的学生的基础研究。他们开发了新的模型来了解基本方面并控制光还原活性。该项目的首要目标是以节能和可持续的方式构建复杂的分子结构。该计划将教学和学习的研究和学术目标结合起来，帮助学生获得实验和智力能力，该计划的更广泛影响包括俄亥俄州西北部的高中生通过名为 PICNICS（家长参与儿童，培养智力好奇心）的外展计划进行的研究。该项目为当地高中三年级和四年级学生提供暑期实习机会，使学生能够亲身了解科学的最新进展，并获得在 BGSU 中心的尖端研究环境中工作的经验。该研究计划制定了指导激发态反应性、发现新的光化学反应性以及通过改变发色团的正常特性来实现反应选择性的策略。反应性发色团的电子特性可以通过内部取代或通过外部添加剂（例如）来改变。这项工作旨在揭示传统系统中未观察到的新光化学途径和反应性，旨在了解分子激发态和分子的反应性、选择性、动力学和寿命之间的微妙平衡。一个目标是利用改变的发色团特性创建与光化学和光物理事件相关的新范例，为以节能和可持续的方式构建具有预定义配置的复杂分子提供了一个平台。研究结果对与光科学相关的基本概念产生了重大影响，并广泛影响了合成、材料科学、有机光电子学、催化和环境科学领域。这项研究为学生培训和公共推广项目中的研究整合提供了机会。反映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，NSF 的法定使命被认为值得支持。

项目成果

Chemoselective light‐induced reactivity of β‐enaminones

化学选择性光诱导β烯胺酮的反应性

• DOI: 10.1111/php.13889
• 发表时间: 2023-11
• 期刊: Photochemistry and Photobiology
• 影响因子: 3.3
• 作者: Valloli, Lakshmy Kannadi;Manal, Kavyasree;Lewis, Brieanna;Jockusch, Steffen;Sivaguru, Jayaraman
• 通讯作者: Sivaguru, Jayaraman

Confinement directed Photoreactivity of β-Enaminones

β-烯胺酮的限制定向光反应性

• DOI: 10.1016/j.jphotochem.2023.115175
• 发表时间: 2024-01
• 期刊: Journal of Photochemistry and Photobiology A: Chemistry
• 作者: Khadka, Dipendra;Kannadi Valloli, Lakshmy;Ramamurthy, V.;Sivaguru, J.
• 通讯作者: Sivaguru, J.

Photochemical [2+4]‐Dimerization Reaction from the Excited State

光化学 [2 4] — 激发态的二聚反应

• DOI: 10.1002/anie.202316662
• 发表时间: 2023-12
• 期刊: Angewandte Chemie International Edition
• 作者: Ahuja, Sapna;Baburaj, Sruthy;Valloli, Lakshmy Kannadi;Rakhimov, Sarvar Aminovich;Manal, Kavyasree;Kushwaha, Aakrati;Jockusch, Steffen;Forbes, Malcolm D. E.;Sivaguru, Jayaraman
• 通讯作者: Sivaguru, Jayaraman

Keeping the name clean: [2 + 2] photocycloaddition

保持名字干净：[2-2] photocycloaddition

• DOI: 10.1007/s43630-022-00239-7
• 发表时间: 2022-04
• 期刊: Photochemical & Photobiological Sciences
• 影响因子: 3.1
• 作者: Sivaguru, Jayaraman;Bach, Thorsten;Ramamurthy, Vaidhyanathan
• 通讯作者: Ramamurthy, Vaidhyanathan

Chemoselective Photoreaction of Enamides: Divergent Reactivity towards [3+2]‐Photocycloaddition vs Paternò–Büchi Reaction †

烯酰胺的化学选择性光反应：[3 2] 的不同反应性 – 光环加成与 Paternà – Büchi 反应 –

• DOI: 10.1111/php.13489
• 发表时间: 2021-11
• 期刊: Photochemistry and Photobiology
• 影响因子: 3.3
• 作者: Kandappa, Sunil Kumar;Kumarasamy, Elango;Singathi, Ravichandranath;Valloli, Lakshmy Kannadi;Ugrinov, Angel;Sivaguru, Jayaraman
• 通讯作者: Sivaguru, Jayaraman