CAREER: Synthesis, Characterization and Reactivity of Iron-Functionalized Polyoxovanadate-Alkoxide Clusters for the Activation of Small Molecules

职业：用于活化小分子的铁官能化多氧钒酸盐-醇盐簇的合成、表征和反应性

基本信息

批准号：
1653195
负责人：
Ellen Matson
金额：
$ 69.11万
依托单位：
University of Rochester
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-07-01 至 2022-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1653195&HistoricalAwards=false
关键词：
CAREER Synthesis Characterization Reactivity Iron

项目摘要

CAREER: Synthesis, Characterization and Reactivity of Iron-Functionalized Polyoxovanadate-Alkoxide Clusters for the Activation of Small MoleculesIn considering the global challenges society faces today, the issue of securing future energy resources is particularly conspicuous. As fossil fuels are depleted, chemists have turned their focus to investigating synthetic methods for obtaining alternative energy resources and producing chemicals. A central challenge to developing such sustainable and renewable strategies is the conversion of abundant, yet unreactive, molecules such as carbon dioxide and nitrogen into useful chemicals that meet societal needs. In Nature, the conversion of these abundant molecules is accomplished by multi-metal assemblies that share and transfer the electrons required to carry out the useful chemical reactions. Drawing inspiration from these systems, Dr. Matson is investigating the electronic interactions between metal-oxide clusters and transition metals. The goal of this project is to understand how transition metals work cooperatively to mediate the multi-electron activation of the strong bonds of chemical pollutants. Dr. Matson is actively engaged in a number of outreach activities in Rochester, building upon her previous training as a chemistry teacher. These events are designed to improve the dissemination of scientific knowledge to young students by increasing exposure through demonstrations and training teachers to be more effective in their communication with students. With funding from the Chemical Synthesis Program of the Chemistry Division of the National Science Foundation, Dr. Matson and her research group are investigating the synthesis and reactivity of a family of iron-functionalized polyoxovandate-alkoxide clusters. These hexanuclear, multi-metallic, Lindqvist clusters possess rich redox chemistry, making them ideal platforms for the mediation of multi-electron transformations pertinent to the activation of small molecules (e.g. CO2. N2, NOx, etc.). In addition to establishing a general synthetic route to access iron-functionalized polyoxovanadate-alkoxide clusters, Dr. Matson is working to develop an understanding of the electronic properties of these delocalized systems through stoichiometric redox reactivity. These research efforts are generating a unique class of metalloligands to support multi-electron transformations using first-row transition metal centers; with a focus on the ability of the metal-oxide framework to serve as a redox-active reservoir. Dr. Matson is actively engaged in multiple outreach initiatives targeted at facilitating dissemination of scientific content to young students. The research and outreach initiatives ongoing in the Matson Lab will lead to significant broader impacts on chemistry education and research within the community.

职业：用于活化小分子的铁官能化多氧钒酸盐-醇盐簇的合成、表征和反应性考虑到当今社会面临的全球挑战，确保未来能源资源的问题尤为突出。随着化石燃料的枯竭，化学家已将注意力转向研究获取替代能源和生产化学品的合成方法。制定此类可持续和可再生战略的一个核心挑战是将二氧化碳和氮气等丰富但不活泼的分子转化为满足社会需求的有用化学品。在自然界中，这些丰富分子的转化是通过多金属组件来完成的，这些组件共享和转移进行有用化学反应所需的电子。从这些系统中汲取灵感，马森博士正在研究金属氧化物簇和过渡金属之间的电子相互作用。该项目的目标是了解过渡金属如何协同作用来介导化学污染物强键的多电子活化。马特森博士在她之前作为化学教师的培训基础上，积极参与罗切斯特的许多外展活动。这些活动旨在通过演示增加科学知识的接触，并培训教师更有效地与学生沟通，从而改善向年轻学生传播科学知识。在美国国家科学基金会化学部化学合成计划的资助下，Matson 博士和她的研究小组正在研究一系列铁官能化多氧钒酸盐-醇盐簇的合成和反应性。这些六核、多金属 Lindqvist 簇具有丰富的氧化还原化学性质，使其成为介导与小分子（例如 CO2、N2、NOx 等）活化相关的多电子转化的理想平台。除了建立获得铁功能化多氧钒酸盐醇盐簇的通用合成路线外，Matson 博士还致力于通过化学计量的氧化还原反应性来了解这些离域系统的电子特性。这些研究工作正在产生一类独特的金属配体，以支持使用第一排过渡金属中心的多电子转化；重点关注金属氧化物框架作为氧化还原活性储层的能力。马森博士积极参与多项旨在促进向年轻学生传播科学内容的外展活动。美森实验室正在进行的研究和推广活动将对社区内的化学教育和研究产生更广泛的影响。

项目成果

期刊论文数量（21）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Mechanistic insights into polyoxometalate self-assembly in organic solvent: conversion of a cyclic polyoxovanadate-ethoxide to its Lindqvist congener

有机溶剂中多金属氧酸盐自组装的机理见解：环状多氧钒酸盐-乙醇盐转化为其 Lindqvist 同系物

DOI：
10.1039/d0cc03464a
发表时间：
2020-07
期刊：
Chemical Communications
影响因子：
4.9
作者：
Meyer, Rachel L.;Love, Robert;Brennessel, William W.;Matson, Ellen M.
通讯作者：
Matson, Ellen M.

Characterizing Polyoxovanadate‐Alkoxide Clusters Using Vanadium K‐Edge X‐Ray Absorption Spectroscopy

使用钒 K 边缘 X 射线吸收光谱表征多氧钒酸盐 - 醇盐簇

DOI：
10.1002/chem.202003625
发表时间：
2020-12
期刊：
Chemistry – A European Journal
影响因子：
0
作者：
Meyer, Rachel L.;Greer, Samuel M.;Blake, Anastasia V.;Cary, Samantha K.;Ditter, Alexander S.;Daly, Scott R.;Li, Feng;Kozimor, Stosh A.;Matson, Ellen M.;Mocko, Veronika;et al
通讯作者：
et al

Mechanistic insight into rapid oxygen-atom transfer from a calix-functionalized polyoxovanadate

杯功能化聚氧钒酸盐快速氧原子转移的机理研究

DOI：
10.1039/d2cc01228f
发表时间：
2022-05
期刊：
Chemical Communications
影响因子：
4.9
作者：
Fertig, Alex. A.;Cooney, Shannon E.;Meyer, Rachel L.;Brennessel, William W.;Matson, Ellen M.
通讯作者：
Matson, Ellen M.

Oxygen-atom vacancy formation and reactivity in polyoxovanadate clusters

多钒酸盐簇中氧原子空位的形成和反应性