Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII

Janneke Ravensbergen, Antaeres Antoniuk-Pablant, Benjamin D. Sherman, Gerdenis Kodis, Jackson D. Megiatto, Dalvin D. Méndez-Hernández, Raoul N. Frese, Rienk Van Grondelle, Thomas Moore, Ana Moore, Devens Gust, John T M Kennis

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Abstract

Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the Tyr<inf>Z</inf>-D<inf>1</inf>His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

Original languageEnglish (US)
Pages (from-to)12156-12163
Number of pages8
JournalJournal of Physical Chemistry B
Volume119
Issue number37
DOIs
StatePublished - Sep 1 2015

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Ravensbergen, J., Antoniuk-Pablant, A., Sherman, B. D., Kodis, G., Megiatto, J. D., Méndez-Hernández, D. D., Frese, R. N., Van Grondelle, R., Moore, T., Moore, A., Gust, D., & Kennis, J. T. M. (2015). Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII. Journal of Physical Chemistry B, 119(37), 12156-12163. https://doi.org/10.1021/acs.jpcb.5b05298