CAREER: Small Molecule Activations Enabled by Coordination-Driven Self-Assembly

职业：通过协调驱动的自组装实现小分子激活

• 批准号: 1847950
• 负责人: Timothy Cook
• 金额: $ 67.5万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1847950&HistoricalAwards=false
• 关键词: CAREER; Small; Molecule; Activations; Enabled

Nature provides many examples of catalysts (molecules that speed reactions up) that contain multiple metal atoms in their active sites. These catalysts are very effective at changing small molecules into more desirable products and play a role in many critical processes, such as photosynthesis and respiration. Understanding how multiple metal atoms can work together requires control over the size and shape of a given catalyst. In this project, Dr. Cook is using self-assembly methods to design highly tunable catalysts in which size and shape can be systematically changed to see how they affect small molecules. His group can change the distance between metal centers, the type of metals present, and the nature of the supporting organic building blocks. The study of these systems provides a deeper understanding of small molecule activations. Ultimately, they may serve as guides for the design of catalysts that enable renewable energy and greener routes to chemical feedstocks. In parallel with this research program, Dr. Cook is using 3D-printing technology as a tool to illustrate self-assembly and other fundamental chemistry concepts with interactive, dynamic models for the classroom. These efforts include a partnership with the Buffalo Public School System to provide research opportunities and professional development for teachers in the design and use of classroom materials.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Cook of the University at Buffalo is using self-assembly as a synthetic methodology to construct architectures in which metal-containing porphyrins, diglyoximes, and related polypyrrole macrocycles serve as catalytically active sites. These self-assembly reactions use metal-ligand bond formation as a driving force to organize cofacial geometries. This synthetic approach provides modularity and control over metal-metal separation, substrate access, structural rigidity, and molecular modifications to tune electronic structure. The role of these parameters on the electrochemical reduction of molecular oxygen, protons and carbon dioxide is being established using activity studies, electrochemical methods, and structural analyses. The resulting information about the structure-activity relationships and mechanistic insight governing selectivity, turnover frequency, and catalyst stability is providing a deeper understanding of small molecule activations. Dr. Cook is actively designing classroom materials for STEM education centered on interactive, dynamic models to illustrate self-assembly and general chemistry concepts for use by high school teachers and undergraduate lecturers. These activities involve the Buffalo Public School System through research opportunities and teacher professional development.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.

《自然》杂志提供了许多催化剂(加速反应的分子)的例子，它们的活性中心含有多个金属原子。这些催化剂在将小分子转化为更理想的产品方面非常有效，并在许多关键过程中发挥作用，如光合作用和呼吸作用。要了解多个金属原子如何协同工作，需要控制给定催化剂的大小和形状。在这个项目中，库克博士正在使用自组装方法设计高度可调的催化剂，这种催化剂的大小和形状可以系统地改变，以观察它们对小分子的影响。他的团队可以改变金属中心之间的距离、存在的金属类型以及支持有机构件的性质。对这些体系的研究有助于更深入地了解小分子的活化作用。最终，它们可能成为催化剂设计的指南，使可再生能源和更环保的化学原料路线成为可能。在这项研究计划的同时，库克博士正在使用3D打印技术作为一种工具，通过互动的、动态的课堂模型来展示自组装和其他基本的化学概念。这些努力包括与布法罗公立学校系统的合作，为教师在设计和使用课堂材料方面提供研究机会和专业发展。在化学系化学催化计划的资助下，布法罗大学的库克博士正在使用自组装作为合成方法来构建结构，其中含有金属的卟啉、二乙二酮肟和相关的聚吡咯大环作为催化活性中心。这些自组装反应使用金属-配位键的形成作为组织界面几何结构的驱动力。这种合成方法提供了模块化和对金属-金属分离、衬底访问、结构刚性和分子修饰的控制，以调整电子结构。这些参数在分子氧、质子和二氧化碳的电化学还原中的作用正在通过活性研究、电化学方法和结构分析来确定。由此产生的关于结构-活性关系和控制选择性、周转频率和催化剂稳定性的机理洞察力的信息提供了对小分子激活的更深层次的理解。库克博士正在积极设计STEM教育的课堂材料，以互动、动态的模型为中心，说明自组装和一般化学概念，供高中教师和本科生讲师使用。这些活动涉及布法罗公立学校系统的研究机会和教师专业发展。该奖项反映了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

The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis

自组装面卟啉的刚性影响氧还原电催化的选择性和动力学

• DOI: 10.1039/d2dt02724k
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Zhang, Daoyang;Crawley, Matthew R.;Fang, Ming;Kyle, Lea J.;Cook, Timothy R.
• 通讯作者: Cook, Timothy R.

Exploring the Emergent Redox Chemistry of Pd(II) Nodes with Pendant Ferrocenes: From Precursors, through Building Blocks, to Self-Assemblies

• DOI: 10.3390/inorganics11030122
• 发表时间: 2023-03-01
• 期刊: INORGANICS
• 影响因子: 2.9
• 作者: Gilbert，Austin B.;Crawley，Matthew R.;Cook，Timothy R.
• 通讯作者: Cook，Timothy R.

Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

• DOI: 10.1021/jacs.0c11895
• 发表时间: 2021-01-20
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Crawley, Matthew R.;Zhang, Daoyang;Cook, Timothy R.
• 通讯作者: Cook, Timothy R.