| Transient Rh L₃-edge X-ray absorption spectroscopy following excitation at 266 nm | Negative intensities were associated with Rh(acac)(CO)₂ ground-state bleach and positive features with induced absorption in characteristic pre-edge peaks |
|---|---|
| Transient Rh L₃-edge X-ray absorption spectroscopy, pre-edge shift | A shift as small as 0.4 eV was observed between 10 and 500 ps |
| Total-fluorescence-yield intensity, global sequential kinetic fit | Time constants of 0.46 ± 0.05 ps, 1.1 ± 0.1 ps and 6.4 ± 0.2 ps represented the lifetimes of the parent excited-state manifold, the monocarbonyl fragment and the C–H σ-complex, respectively; R² = 0.989 |
| Transient Rh L₃-edge X-ray absorption spectroscopy and sequential kinetic model, 250 fs | ~58 % excited-state species, ~37 % monocarbonyl fragment and ~5 % σ-complex; pre-edge position 3003 eV |
| Transient Rh L₃-edge X-ray absorption spectroscopy and sequential kinetic model, 2 ps | σ-complex 63 %, residual monocarbonyl fragment 26 % and nitrogen-coordinated solvent complex 11 %; the pre-edge peak shifted by ~1 eV to 3004.2 eV and decreased in intensity |
| Transient Rh L₃-edge X-ray absorption spectroscopy and sequential kinetic model, 10 ps | σ-complex 27 % and nitrogen-coordinated solvent complex 73 % |
Timo Dederichs, Raphael M. Jay, Emiliano De Santis, Paulina Aviles, Moritz Dybowski, Tae Gyun Woo, Soo Min Cho, Haneol Oh, Junho Lee, Rory Ma, Yujin Kim, Dogeun Jang, Minseok Kim, Ambar Banerjee, Jae Hyuk Lee, Carl Caleman, Nils Huse, Tae Kyu Kim, Philippe Wernet. “Electrostatic pre-solvation enables selectivity in photoinduced ligand exchange.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15008002/v1
The transient X-ray absorption spectra and time traces in the main paper, pp. 3–4, were not transcribed; their source-written fit and spectral results are retained below. The main paper refers to supporting information, but no separate supporting information file was available on the ChemRxiv article page