Geometry-Independent Ultrafast Energy Transfer in Bioinspired Arrays Containing Electronically Coupled BODIPY Dimers as Energy Donors
Author/Creator
Author/Creator ORCID
Date
Type of Work
Department
Program
Citation of Original Publication
Ansteatt, Sara, Rachel Gelfand, Matthew Pelton, and Marcin Ptaszek. “Geometry-Independent Ultrafast Energy Transfer in Bioinspired Arrays Containing Electronically Coupled BODIPY Dimers as Energy Donors.” Chemistry – A European Journal 29, no. 58 (2023): e202301571. https://doi.org/10.1002/chem.202301571.
Rights
This is the peer reviewed version of the following article: Ansteatt, Sara, Rachel Gelfand, Matthew Pelton, and Marcin Ptaszek. “Geometry-Independent Ultrafast Energy Transfer in Bioinspired Arrays Containing Electronically Coupled BODIPY Dimers as Energy Donors.” Chemistry – A European Journal 29, no. 58 (2023): e202301571. https://doi.org/10.1002/chem.202301571., which has been published in final form at https://doi.org/10.1002/chem.202301571. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Abstract
In photosynthetic light-harvesting complexes, strong interaction between chromophores enables efficient absorption of solar radiation and has been suggested to enable ultrafast energy funneling to the reaction center. To examine whether similar effects can be realized in synthetic systems, and to determine the mechanisms of energy transfer, we synthesized and characterized a series of bioinspired arrays containing strongly-coupled BODIPY dimers as energy donors and chlorin derivatives as energy acceptors. The BODIPY dimers feature broad absorption in the range of 500–600 nm, complementing the chlorin absorption to provide absorption across the entire visible spectrum. Ultrafast (~ 10 ps) energy transfer was observed from photoexcited BODIPY dyads to chlorin subunits. Surprisingly, the energy-transfer rate is nearly independent of the position where the BODIPY dimer is attached to the chlorin and of the type of connecting linker. In addition, the energy-transfer rate from BODIPY dimers to chlorin is slower than the corresponding rate in arrays containing BODIPY monomers. The lower rate, corresponding to less efficient through-bond transfer, is most likely due to weaker electronic coupling between the ground state of the chlorin acceptor and the delocalized electronic state of the BODIPY dimer, compared to the localized state of a BODIPY monomer.