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Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex

Whited, Matthew T. and Djurovich, Peter I. and Roberts, Sean T. and Durrell, Alec C. and Schlenker, Cody W. and Bradforth, Stephen E. and Thompson, Mark E. (2011) Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex. Journal of the American Chemical Society, 133 (1). pp. 88-96. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20140403-163634083

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Abstract

Multichromophoric arrays provide one strategy for assembling molecules with intense absorptions across the visible spectrum but are generally focused on systems that efficiently produce and manipulate singlet excitations and therefore are burdened by the restrictions of (a) unidirectional energy transfer and (b) limited tunability of the lowest molecular excited state. In contrast, we present here a multichromophoric array based on four boron dipyrrins (BODIPY) bound to a platinum benzoporphyrin scaffold that exhibits intense panchromatic absorption and efficiently generates triplets. The spectral complementarity of the BODIPY and porphryin units allows the direct observation of fast bidirectional singlet and triplet energy transfer processes (k_(ST)(^1BDP→^1Por) = 7.8 × 10^(11) s^(−1), k_(TT)(^3Por→^3BDP) = 1.0 × 10^(10) s^(−1), k_(TT)(^3BDP→^3Por) = 1.6 × 10^(10) s^(−1)), leading to a long-lived equilibrated [^3BDP][Por]⇔[BDP][^3Por] state. This equilibrated state contains approximately isoenergetic porphyrin and BODIPY triplets and exhibits efficient near-infrared phosphorescence (λ_(em) = 772 nm, Φ = 0.26). Taken together, these studies show that appropriately designed triplet-utilizing arrays may overcome fundamental limitations typically associated with core−shell chromophores by tunable redistribution of energy from the core back onto the antennae.


Item Type:Article
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http://dx.doi.org/10.1021/ja108493bDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja108493bPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja108493bPublisherSupporting Information
Additional Information:Copyright © 2010 American Chemical Society. Received September 20, 2010. Publication Date (Web): December 10, 2010. Funding for this research was provided by the Center for Advanced Molecular Photovoltaics (CAMP) (KUS-C1-015-21) of the King Abdullah University of Science and Technology (KAUST) and the Global Photonic Corporation. The quantification of absorbance at AM1.5G illumination and femtosecond transient absorption measurements were carried out with support from the Department of Energy’s Energy Frontier Research Center program (Center for Energy Nanoscience, Award DE-SC0001011). S.T.R. acknowledges support from the National Science Foundation in the form of an ACC-F fellowship (CHE-0937015), and A.C.D. acknowledges support from the NSF Center for Chemical Innovation (CCI Powering the Planet, Grants CHE-0802907 and CHE-0947829). We are also grateful to Dr. Jay Winkler and the Beckman Institute Laser Resource Center at the California Institute of Technology for assistance with nanosecond transient absorption measurements. We dedicate this manuscript to Professor Harry B. Gray, pioneer of inorganic photochemistry, on the occasion of his 75th birthday. Supporting Information: Derivation of eq 1; 1H NMR spectrum of 4; absorption and photoluminescence spectra for 3, 4, and model complexes; femtosecond-resolved transient absorption spectra for 3. This material is available free of charge via the Internet at http://pubs.acs.org.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
Center for Advanced Molecular Photovoltaics (CAMP) of the King Abdullah University of Science and Technology (KAUST)KUS-C1-015-21
Global Photonic CorporationUNSPECIFIED
Center for Energy NanoscienceDE-SC0001011
NSFCHE-0937015
NSF Center for Chemical Innovation Powering the PlanetCHE-0802907
NSF Center for Chemical Innovation Powering the PlanetCHE-0947829
Record Number:CaltechAUTHORS:20140403-163634083
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140403-163634083
Official Citation:Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex Matthew T. Whited, Peter I. Djurovich, Sean T. Roberts, Alec C. Durrell, Cody W. Schlenker, Stephen E. Bradforth, and Mark E. Thompson Journal of the American Chemical Society 2011 133 (1), 88-96
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44654
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:04 Apr 2014 14:36
Last Modified:04 Apr 2014 14:36

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