| NSF Org: |
CHE Division Of Chemistry |
| Recipient: |
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| Initial Amendment Date: | January 13, 2017 |
| Latest Amendment Date: | June 23, 2021 |
| Award Number: | 1653195 |
| Award Instrument: | Continuing Grant |
| Program Manager: |
John Gilje
CHE Division Of Chemistry MPS Directorate for Mathematical and Physical Sciences |
| Start Date: | July 1, 2017 |
| End Date: | June 30, 2022 (Estimated) |
| Total Intended Award Amount: | $691,073.00 |
| Total Awarded Amount to Date: | $748,084.00 |
| Funds Obligated to Date: |
FY 2018 = $303,699.00 FY 2021 = $34,428.00 |
| History of Investigator: |
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| Recipient Sponsored Research Office: |
910 GENESEE ST ROCHESTER NY US 14611-3847 (585)275-4031 |
| Sponsor Congressional District: |
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| Primary Place of Performance: |
518 Hylan Building Rochester NY US 14627-0140 |
| Primary Place of
Performance Congressional District: |
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| Unique Entity Identifier (UEI): |
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| Parent UEI: |
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| NSF Program(s): |
OFFICE OF MULTIDISCIPLINARY AC, Chemical Synthesis |
| Primary Program Source: |
01001819DB NSF RESEARCH & RELATED ACTIVIT 01002122DB NSF RESEARCH & RELATED ACTIVIT |
| Program Reference Code(s): |
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| Program Element Code(s): |
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| Award Agency Code: | 4900 |
| Fund Agency Code: | 4900 |
| Assistance Listing Number(s): | 47.049 |
ABSTRACT
CAREER: Synthesis, Characterization and Reactivity of Iron-Functionalized Polyoxovanadate-Alkoxide Clusters for the Activation of Small Molecules
In 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.
PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH
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PROJECT OUTCOMES REPORT
Disclaimer
This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.
Intellectual Merit. Funding from the NSF has supported the development of a research program focused on the synthesis, characterization, and reactivity of site-differentiated POV-alkoxide clusters. While the original proposal emphasized focus on iron-functionalized assemblies, our studies expanded to include the synthesis and reactivity of other metal-substituted vanadium oxide assemblies, as well as a family of oxygen deficient POV-alkoxide clusters. The common theme underlying all work supported through this CAREER award is the development of an understanding of cooperative multielectron reactivity mediated by redox active POV-alkoxide clusters at site differentiated metal centers embedded within the assembly. Key outcomes from the project are summarized below.
The original concept for the proposed studies focused on the development of iron-functionalized POV-alkoxide (FePOV-alkoxide) clusters, where the electroactive vanadium oxide assembly could function as a redox active metalloligand for the site-differentiated metal center. Early success was demonstrated through the synthesis and characterization of FePOV-alkoxide clusters. Studies confirmed that redox chemistry is localized to the vanadium oxide metalloligand, with the iron center retaining its trivalent oxidation state across all five charge states of the heterometallic assembly. We have also demonstrated cooperative reactivity through explorations of the reactivity of the FePOV-alkoxide clusters with nitric oxide; substrate coordination to iron resulted in oxidation of the vanadium oxide portion of the heterometallic assembly, demonstrating a rare example of e- transfer within a multimetallic assembly for small molecule activation.
Our interest in modelling metal oxide materials through use of polyoxovanadate-alkoxide (POV-alkoxide) clusters was initiated through a serendipitous discovery during investigations of the reactivity of FePOV-alkoxide clusters. We observed that O-atoms can be cleaved from the surface of the cluster in the presence of an appropriate reductant, resulting in the formation of an oxygen-deficient, reduced vanadium(III) ion at the surface of the assembly. In a series of reports, we have summarized the reactivity of oxygen deficient POV-alkoxide clusters with dioxygen. Similarly, we have reported the reduction of nitrite and nitrate. Our work has also probed O-atom transfer reactions with relevance to the development of new methodologies in organic synthesis; we have demonstrated that our oxygen deficient POV-alkoxide clusters are capable of converting of oxirene rings to alkenes.
Broader Impact. The major outreach initiative of this CAREER proposal focused on the development of an annual community engagement activity for the Department of Chemistry at UR. Prior to Matson’s arrival at UR, limited opportunities for interaction with elementary-level classrooms in the Rochester City School District (RCSD) were available on campus. Over the five years of funding, Matson developed close ties with a number of participating classrooms across RCSD (Grades K-6). In an average year, 70 volunteers from the Department of Chemistry visited a total of 32 classrooms, exposing over 650 students to age-appropriate science experiments. Unfortunately, we were unable to offer this program in 2020 and 2021, due to the COVID-19 pandemic. We plan to reinitiate the program in Fall 2022.
To supplement this outreach initiative, the PI developed a general studies course entitled “Chemistry Engagement in RCSD (CAS 207)” in partnership with the Rochester Center for Community Leadership. This course guides undergraduate students through the creation and implementation of educational experiences promoting access to science technology engineering and mathematics for RCSD students. The course culminates with undergraduate students teaching a 40-minute lesson. CAS 207 students also trained and supported other undergraduate student volunteers in lesson plan implementation, increasing our program’s impact and visibility.
Last Modified: 10/29/2022
Modified by: Ellen M Matson
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