| NSF Org: |
CHE Division Of Chemistry |
| Recipient: |
|
| Initial Amendment Date: | May 23, 2019 |
| Latest Amendment Date: | May 23, 2019 |
| Award Number: | 1904650 |
| Award Instrument: | Standard Grant |
| Program Manager: |
Tomislav Pintauer
tompinta@nsf.gov (703)292-7168 CHE Division Of Chemistry MPS Direct For Mathematical & Physical Scien |
| Start Date: | June 1, 2019 |
| End Date: | May 31, 2023 (Estimated) |
| Total Intended Award Amount: | $342,669.00 |
| Total Awarded Amount to Date: | $342,669.00 |
| Funds Obligated to Date: |
|
| History of Investigator: |
|
| Recipient Sponsored Research Office: |
3720 S FLOWER ST FL 3 LOS ANGELES CA US 90033 (213)740-7762 |
| Sponsor Congressional District: |
|
| Primary Place of Performance: |
837 Bloom Walk, LHI 105 Los Angeles CA US 90089-1661 |
| Primary Place of
Performance Congressional District: |
|
| Unique Entity Identifier (UEI): |
|
| Parent UEI: |
|
| NSF Program(s): | Macromolec/Supramolec/Nano |
| Primary Program Source: |
|
| Program Reference Code(s): |
|
| Program Element Code(s): |
|
| Award Agency Code: | 4900 |
| Fund Agency Code: | 4900 |
| Assistance Listing Number(s): | 47.049 |
ABSTRACT
With this award, the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry is funding Dr. Barry C. Thompson from the University of Southern California to develop green and energy efficient methods to produce semiconducting polymers. This existing class of plastic-electronic materials has shown great promise for use in organic solar cells and light emitting diodes, as well as several sensory applications in which light is converted to electrical current. In this work, semiconducting polymers are prepared using catalysts based on inexpensive and abundant elements such as copper and nickel. These metals are utilized to lower the energy barrier associated with polymerization processes, making it easier to convert starting materials to desired products. Consequently, their use improves the sustainability of semiconducting polymers and enables new reactivity and properties in the polymers. The new processes associated with this award provide means to assemble the repeating monomer units along main polymer chains in several different ways giving rise not only to linear chains composed of identical repeating units, but also chains in which those repeating units are different and arranged in controlled and predictable ways. Consequently, access to such advanced architectures in these polymers could lead to improvements in their applications, specifically the efficiency by which they convert sunlight into electricity. The work enables outstanding training for undergraduate and graduate students in polymer chemistry, extending to students hosted at the University of Southern California from Cerritos Community College. The broad impact through the development of a graduate student exchange program with Ludwig Maximillians University in Munich, Germany is very important for helping to expose students to the broader scope of international research and collaboration.
This research is focused on the development of alternative synthetic routes to direct arylation polymerization catalyzed by copper and nickel complexes for the synthesis of conjugated, semiconducting polymers. Special emphasis is also placed on the use of green and environmentally friendly solvents. The capabilities of direct arylation polymerization are extended by focusing toward a transition from step-growth to chain-growth, which enables access to more advanced architectures such as block and gradient copolymers. Studies related to the ability of direct arylation polymerization to effect controlled living polymerization are a significant step forward in this area of research because it would enable control over the molecular weight and polymer polydispersity. An additional direction involves exploration of more sustainable oxidants for the related dehydrogenative polymerization process that avoids monomer halogenation and the use of stoichiometric amounts of silver oxidants. The use of earth-abundant copper and nickel catalysts to access conjugated polymers via this work is important and has the potential to significantly reduce the cost and complexity of existing procedures for conjugated polymer synthesis, which are generally not atom efficient, require harsh reaction conditions, toxic solvents, and create significant amounts of waste products.
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.
PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH
Note:
When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external
site maintained by the publisher. Some full text articles may not yet be available without a
charge during the embargo (administrative interval).
Some links on this page may take you to non-federal websites. Their policies may differ from
this site.
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.
Organic electronics continue to gain momentum as an emerging class of materials with potential applications in bioelectronics and alternative energy. With growing interest and demand, sustainable methods for the synthesis of semiconducting, conducting, and redox active organic materials are highly sought after. Conjugated organic polymers are the predominant material class and prevailing synthetic methods often invoke toxic reagents, unsustainable solvents, and rare metals as catalysts. Direct Arylation Polymerization (DArP) has emerged as a sustainable alternative for the synthesis of these high value and potentially broadly impactful materials.
Intellectual Merit. The key focus of this work was to not only enhance the sustainability of the DArP reaction but to expand the performance and capabilities of the method in order to exceed prevailing methods both in sustainability and efficacy for achieving desired targets. Specifically, this work led to a series of breakthroughs in the use of green solvents, where p-cymene was identified as a benign renewable solvent (e.g., found in lemon peels) that is effective for the DArP reaction. Additionally, the first report of DArP in aqueous emulsion conditions was reported, which is practical for scale-up of polymerizations. The first report demonstrating the multiple recycling of heterogeneous catalysts in DArP also resulted from the work in this project. Such an approach limits the cost of DArP by allowing expensive and rare metal-based catalysts (e.g., palladium-based) to be re-used for multiple batch polymerizations. Likewise, the successful use of copper catalysts demonstrated an alternative to the use of rare elements such as palladium.
Broader Impacts. Community college students from Cerritos Community College were hosted at USC as summer researchers. These students (primarily from under-represented groups) gained valuable exposure to high level research. Efforts toward developing write-to-learn (WTL) pedagogies were also explored in large undergraduate courses at USC. Finally, an international collaboration with German colleagues was targeted for an international graduate student exchange.
Last Modified: 09/23/2023
Modified by: Barry C Thompson
Please report errors in award information by writing to: awardsearch@nsf.gov.
