CAS: Near-Infrared Light Control of Metal Catalyzed Reactions and Polymerizations

CAS：金属催化反应和聚合的近红外光控制

• 批准号: 2102672
• 负责人: Tomislav Rovis
• 金额: $ 50万
• 依托单位: Columbia University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102672&HistoricalAwards=false
• 关键词: CAS; Near; Infrared; Light; Control

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Tomislav Rovis of Columbia University is studying the use of near-infrared (NIR) light to control catalysts that mediate a number of fundamental chemical reactions. Catalysis is a technology of prime importance and has deep implications in many fields, ranging from synthetic chemistry to the production and manufacturing of pharmaceuticals, fine and commodity materials, as well as new well-defined materials. Indeed, it is estimated that 85% of all products made involve catalysis at some point in their production. Most work on the development of new catalytic systems focus on aspects related to efficiency and selectivity. The notion of spatial and temporal control has been largely under-studied and remains elusive. Of all possible stimuli to achieve control, light is the most attractive since it is noninvasive, it can be easily manipulated thanks to modern optics techniques. NIR light is particularly suitable as it can penetrate materials and induce reactions through barriers. This can be attractive to the plastics industry, as it allows the shaping of highly controllable yet robust materials through molds. The project will establish the use of NIR light to control polymerizations through material barriers with an eye towards achieving new technological breakthroughs to enable, enhance, and drive plastics and material science. The project will also create the opportunity to synthesize a set of industrially recyclable, environmentally benign polymers from which the monomer can be regenerated and reused. Additionally, educational opportunities will be provided for underrepresented students, from elementary school students to undergraduates, to broaden interest and educate them in photochemistry and polymerization. With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Tomislav Rovis of Columbia University is studying the use of near-infrared (NIR) light to activate various catalysts to effect catalyzed polymerizations through barriers. The project will establish NIR control of ruthenium-catalyzed olefin metathesis reactions for the spatiotemporal controlled synthesis of polyolefin-like structures. Inherent to the approach is the propensity of low-energy NIR light to penetrate material barriers such as silicone, paper, plastic and even tissue. The project aims to take maximum advantage of the energy of NIR light to induce chemical change at the catalyst of interest. This research has he potential to greatly enhance fundamental understanding of the mechanism of NIR-initiated olefin metathesis. Extensions of this work will include orthogonal light and heat polymerization and depolymerization along with in situ studies for bioimaging. With this approach, the project will also extend into other NIR-controlled polymerizations, including N-heterocyclic carbene activation to induce polymerization en route to polyurethanes and polyesters, two crucial families of organic materials. Finally, the project will establish a visible demonstration of NIR-enabled polymerizations that will be used to teach catalysis, central to so many facets of everyday life, to broaden awareness of fundamental science.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.

在化学系化学催化项目的支持下，哥伦比亚大学的Tomislav Rovis教授正在研究使用近红外（NIR）光来控制催化剂，这些催化剂介导了许多基本的化学反应。催化是一项至关重要的技术，在许多领域都有着深远的影响，从合成化学到药品、精细和商品材料以及新的明确定义的材料的生产和制造。事实上，据估计，85%的产品在生产过程中的某个时候涉及催化。开发新催化系统的大多数工作集中在与效率和选择性有关的方面。空间和时间控制的概念在很大程度上研究不足，仍然难以捉摸。在实现控制的所有可能的刺激中，光是最有吸引力的，因为它是非侵入性的，由于现代光学技术，它可以很容易地被操纵。NIR光是特别合适的，因为它可以穿透材料并通过屏障诱导反应。这对塑料行业来说很有吸引力，因为它允许通过模具成型高度可控但坚固的材料。该项目将利用近红外光来控制穿过材料屏障的聚合反应，以期实现新的技术突破，以实现、增强和推动塑料和材料科学。该项目还将创造机会，合成一套工业可回收，环境友好的聚合物，单体可以再生和重复使用。此外，将为从小学生到大学生的代表性不足的学生提供教育机会，以扩大他们的兴趣，并教育他们光化学和聚合。 在化学系化学催化计划的支持下，哥伦比亚大学的Tomislav Rovis教授正在研究使用近红外（NIR）光来激活各种催化剂，以实现催化聚合。该项目将建立对钌催化的烯烃复分解反应的近红外控制，用于聚烯烃类结构的时空控制合成。该方法的固有特性是低能量近红外光倾向于穿透材料屏障，如硅胶，纸张，塑料甚至纸巾。该项目旨在最大限度地利用近红外光的能量，在感兴趣的催化剂上引发化学变化。这项研究有可能大大提高对近红外引发烯烃复分解反应机理的基本理解。这项工作的扩展将包括正交光和热聚合和解聚沿着与原位研究的生物成像。通过这种方法，该项目还将扩展到其他NIR控制的聚合反应，包括N-杂环卡宾活化以诱导聚氨酯和聚酯这两种重要有机材料家族的聚合反应。最后，该项目将建立一个可见的近红外聚合示范，将用于教授催化，对日常生活的许多方面至关重要，以扩大对基础科学的认识。该奖项反映了NSF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。

项目成果

Deep Red to Near-Infrared Light-Controlled Ruthenium-Catalyzed Olefin Metathesis

• DOI: 10.1021/acscatal.3c00473
• 发表时间: 2023-04-07
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Cabanero, David C.;Nguyen, Jennifer A.;Rovis, Tomislav
• 通讯作者: Rovis, Tomislav