A charge transfer state induced by strong exciton coupling in a cofacial μ-oxo-bridged porphyrin heterodimer

Niloofar Zarrabi, Brandon J Bayard, Sairaman Seetharaman, Noah Holzer, Paul Karr, Susanna Ciuti, Antonio Barbon, Marilena Di Valentin, Art Van Der Est, Francis D'Souza, Prashanth K. Poddutoori

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

Photosensitizers with high energy, long lasting charge-transfer states are important components in systems designed for solar energy conversion by multistep electron transfer. Here, we show that in a push-pull type, μ-oxo-bridged porphyrin heterodimer composed of octaethylporphyrinatoaluminum(iii) and octaethylporphyrinatophosphorus(v), the strong excitonic coupling between the porphyrins and the different electron withdrawing abilities of Al(iii) and P(v) promote the formation of a high energy CT state. Using, an array of optical and magnetic resonance spectroscopic methods along with theoretical calculations, we demonstrate photodynamics of the heterodimer that involves the initial formation of a singlet CT which relaxes to a triplet CT state with a lifetime of ∼130 ps. The high-energy triplet CT state (3CT = 1.68 eV) lasts for nearly 105 μs prior to relaxing to the ground state.

Original languageEnglish (US)
Pages (from-to)960-970
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number2
DOIs
StatePublished - Jan 21 2021

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