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Delayed fluorescence from a zirconium(IV) photosensitizer with ligand-to-metal charge-transfer excited states.

08:00 EDT 16th March 2020 | BioPortfolio

Summary of "Delayed fluorescence from a zirconium(IV) photosensitizer with ligand-to-metal charge-transfer excited states."

Advances in chemical control of the photophysical properties of transition-metal complexes are revolutionizing a wide range of technologies, particularly photocatalysis and light-emitting diodes, but they rely heavily on molecules containing precious metals such as ruthenium and iridium. Although the application of earth-abundant 'early' transition metals in photosensitizers is clearly advantageous, a detailed understanding of excited states with ligand-to-metal charge transfer (LMCT) character is paramount to account for their distinct electron configurations. Here we report an air- and moisture-stable, visible light-absorbing Zr(IV) photosensitizer, Zr(PDP), where [PDP] is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. This molecule has an exceptionally long-lived triplet LMCT excited state (τ = 350 μs), featuring highly efficient photoluminescence emission (Ф = 0.45) due to thermally activated delayed fluorescence emanating from the higher-lying singlet configuration with significant LMCT contributions. Zr(PDP) engages in numerous photoredox catalytic processes and triplet energy transfer. Our investigation provides a blueprint for future photosensitizer development featuring early transition metals and excited states with significant LMCT contributions.

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This article was published in the following journal.

Name: Nature chemistry
ISSN: 1755-4349
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