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Pump-probe XAS investigation of the triplet state of Ir photosensitizer with chromenopyridinone ligands

Abstract

The triplet excited state of a new Ir-based photosensitizer with two chromenopyridinone and one bipyridine-based ligands has been studied by pump-probe X-ray absorption near edge structure (XANES) spectroscopy coupled with DFT calculations. The excited state has a lifetime of 0.5 µs in acetonitrile and is characterized by very small changes of the local atomic structure with an average metal-ligand bond length change less than 0.01 Å. DFT-based calculations allow interpretation of the XANES in the energy range of ~50 eV around the absorption edge. The observed transient XANES signal arises from an additional metal-centered Ir 5d vacancy in the excited state which appears as a result of electron transfer from the metal to the ligand. The overall energy shift of the excited state spectrum originates from the shift of 2p and unoccupied states induced by screening effects. The approach for the analysis of time-resolved spectra of 5d metal complexes is quite general and can be also used if excited and ground state structures are significantly different.

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Publication details

The article was received on 13 Feb 2018, accepted on 12 May 2018 and first published on 14 May 2018


Article type: Paper
DOI: 10.1039/C8PP00065D
Citation: Photochem. Photobiol. Sci., 2018, Accepted Manuscript
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    Pump-probe XAS investigation of the triplet state of Ir photosensitizer with chromenopyridinone ligands

    G. Smolentsev, K. M. van Vliet, N. Azzaroli, J. van Bokhoven, A. M. Brouwer, B. de Bruin, M. Nachtegaal and M. Tromp, Photochem. Photobiol. Sci., 2018, Accepted Manuscript , DOI: 10.1039/C8PP00065D

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