Sb(<scp>v</scp>) dihalide corroles: efficient singlet oxygen photosensitisers

Caliskanyürek, Volkan; Eulberg, Simon; Lange, Oliver; Bröring, Martin; Tschierlei, Stefanie

doi:10.1039/d4cc00675e

Chem. Commun.

2024

DOI: 10.1039/d4cc00675e

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Sb(v) dihalide corroles: efficient singlet oxygen photosensitisers

Volkan Caliskanyürek,

Simon Eulberg,

Oliver Lange

et al.

Abstract: Sb(V) dihalide corrole complexes, , in particular difluoro-5,15-di(4-cyanophenyl)-10-(2,4,5-trimethoxyphenyl)corrolatoantimon(V) (complex 1), show distinct emission properties and efficient intersystem crossing rates. Furthermore, complex 1 is characterised by its extended triplet excited state...

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Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions

Caliskanyürek,

Riabchunova,

Kupfer

et al. 2024

Inorg. Chem.

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Three homoleptic Al(III) complexes (Al1–Al3) with different degrees of methylation at the 2-pyridylpyrrolide ligand were systematically tested for their function as photosensitizers (PS) in two types of energy transfer reactions. First, in the generation of reactive singlet oxygen (1O2), and second, in the isomerization of (E)- to (Z)-stilbene. 1O2 was directly evidenced by its characteristic NIR emission at around 1276 nm and indirectly by the reaction with an organic substrate [e.g. 2,5-diphenylfuran (DPF)] using in situ UV/vis spectroscopy. In a previous study, the presence of additional methyl groups was found to be beneficial for the photocatalytic reduction of CO2 to CO, but here Al1 without any methyl groups exhibits superior performance. To rationalize this behavior, a combination of photophysical experiments (absorption, emission and excited state lifetimes) together with photostability measurements and scalar-relativistic time-dependent density functional theory calculations was applied. As a result, Al1 exhibited the highest emission quantum yield (64%), the longest emission lifetime (8.7 ns) and the best photostability under the reaction conditions required for the energy transfer reactions (e.g. in aerated chloroform). Moreover, Al1 provided the highest rate constant (0.043 min–1) for the photocatalytic oxygenation of DPF, outperforming even noble metal-based competitors such as [Ru(bpy)3]2+. Finally, its superior photostability enabled a long-term test (7 h), in which Al1 was successfully recycled seven times, underlining the high potential of this new class of earth-abundant PSs.

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Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions

Caliskanyürek,

Riabchunova,

Kupfer

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

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Sb(v) dihalide corroles: efficient singlet oxygen photosensitisers

Cited by 1 publication

References 24 publications

Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions

Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions

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