Resumen
The rate of singlet fission, the process of generating two triplet excitons with photoexcitation of one singlet exciton, depends on a combination of singlet/triplet energy balance and intermolecular coupling. Here, we perform carboxylic acid functionalization of anthradithiophene (ADT) derivatives that results in hydrogen bonds that drive molecular orientation and strong electronic coupling of polycrystalline ADT thin films, leading to ultrafast singlet fission without significant enthalpic driving force. ADT with a single carboxylic acid group exhibits weak intermolecular coupling and slow and inefficient singlet fission, much like the parent ADT, and substitution of different alkylsilyl solubilizing groups has little effect. However, the addition of two carboxylic acid groups on either end of the long axis favors significant coupling and crystallinity in as-deposited thin films that increase the effective singlet fission rate by roughly three orders of magnitude. The properties of the triplet pair, particularly its propensity to form long-lived independent triplets, are also influenced by the degree of long-range intermolecular coupling. The enhancement of intermolecular coupling specific to singlet fission using the ubiquitous cyclic hydrogen bonding motif could impact triplet pair utilization schemes in a variety of contexts.
| Idioma original | English |
|---|---|
| Páginas (desde-hasta) | 68-78 |
| Número de páginas | 11 |
| Publicación | ChemPhotoChem |
| Volumen | 5 |
| N.º | 1 |
| DOI | |
| Estado | Published - ene 2021 |
Nota bibliográfica
Publisher Copyright:© 2020 Wiley-VCH GmbH
Financiación
This work was authored by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided by U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Synthetic efforts were supported by the National Science Foundation under Cooperative Agreement No. 1849213. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This work was authored by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE‐AC36‐08GO28308. Funding provided by U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Synthetic efforts were supported by the National Science Foundation under Cooperative Agreement No. 1849213. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe‐public‐access‐plan ).
| Financiadores | Número del financiador |
|---|---|
| DOE Public Access Plan | |
| Chemical Sciences, Geosciences, and Biosciences Division | |
| U.S. Government | |
| National Science Foundation (NSF) | 1849213 |
| Michigan State University-U.S. Department of Energy (MSU-DOE) Plant Research Laboratory | DE‐AC36‐08GO28308 |
| Office of Basic Energy Sciences | |
| National Renewable Energy Laboratory |
ASJC Scopus subject areas
- Analytical Chemistry
- Physical and Theoretical Chemistry
- Organic Chemistry