Musser, A.J. orcid.org/0000-0002-4600-6606, Neelakandan, P.P., Richter, J.M. et al. (3 more authors) (2017) Excitation Energy Delocalization and Transfer to Guests within M(II)4L6 Cage Frameworks. Journal of the American Chemical Society, 139 (34). pp. 12050-12059. ISSN 0002-7863
Abstract
We have prepared a series of M(II)4L6 tetrahedral cages containing one or the other of two distinct BODIPY moieties, as well as mixed cages that contain both BODIPY chromophores. The photophysical properties of these cages and their fullerene-encapsulated adducts were studied in depth. Upon cage formation, the charge-transfer character exhibited by the bis(aminophenyl)-BODIPY subcomponents disappeared. Strong excitonic interactions were instead observed between at least two BODIPY chromophores along the edges of the cages, arising from the electronic delocalization through the metal centers. This excited-state delocalization contrasts with previously reported cages. All cages exhibited the same progression from an initial bright singlet state (species I) to a delocalized dark state (species II), driven by interactions between the transition dipoles of the ligands, and subsequently into geometrically relaxed species III. In the case of cages loaded with C60 or C70 fullerenes, ultrafast host-to-guest electron transfer was observed to compete with the excitonic interactions, short-circuiting the I → II → III sequence.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Physics and Astronomy (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 06 Sep 2017 13:24 |
Last Modified: | 30 Oct 2017 09:24 |
Published Version: | https://doi.org/10.1021/jacs.7b06709 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.7b06709 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:120868 |