Ultrafast relaxation processes in photoactive heteroleptic copper(I) complexes: insights into the interplay between excited states.

30 March 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The developments made towards increasingly photoactive copper(I) complexes has led to their use in many applications involving light, in particular light emission or photocatalytic activities. Herein, we describe an unprecedented in-depth study of the photophysical properties of two of the most used copper(I) photosensitizers, [Cu(bcp)(Xantphos)]+ and [Cu(bcp)(DPEphos)]+ (bcp = bathocuproine, Xantphos = 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene, DPEphos = Bis[(2-diphenylphosphino)phenyl]ether). This study combines traditional spectroscopic techniques with state-of-the-art femtosecond time-resolved transient absorption and fluorescence up-conversion spectroscopy and is further supported by quantum-chemical calculations. This combined analysis hints at the presence of a low-lying ligand-centered dark triplet state which plays a crucial role by acting as a reservoir for the excited hetereloptic copper(I) complexes.


Time-resolved spectroscopy
Molecular modelling

Supplementary materials

Ultrafast relaxation processes in photoactive heteroleptic copper(I) complexes.
The supplementary files contains additional data not shown directly in the paper as well as the optimized geometries of the compounds.


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