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A Charge Transfer State Induced by Strong Exciton Coupling in a Cofacial μ-Oxo-bridged Porphyrin Heterodimer by 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 is a Chemistry article available to read on EtoBox.

What is A Charge Transfer State Induced by Strong Exciton Coupling in a Cofacial μ-Oxo-bridged Porphyrin Heterodimer about?

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.

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Author

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

Publisher

Royal Society of Chemistry; The Royal Society of Chemistry; Royal Society of Chemistry (RSC) (ISSN 1463-9076)

Published

2021

Language

EN

Field

Chemistry (Physical Sciences)