Probing Molecular Chirality from Vibrational to X-ray Energies in Cr(III) and Co(III) Complexes
- 1CNRS
- 2CNRS, UMR, 4 place Jussieu, Paris cedex, France, F-75252
- 3European Synchrotron Radiation Facility (ESRF
Abstract
The expression of molecular chirality across widely separated energy regimes was investigated in enantiomeric Cr(III) and Co(III) tris(trans-1,2-cyclohexanediamine) complexes using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and X-ray natural circular dichroism (XNCD), supported by single-crystal X-ray diffraction and density functional theory (DFT). Crystallographic analysis establishes the Λ-δδδ/lel3 and Δ-λλλ/lel3 configurations in the solid state, while the ECD spectra and comparison of experimental and DFT-calculated VCD spectra support retention of the lel3 stereochemical arrangement in solution. At the Co K-edge, pronounced opposite-sign XNCD responses are observed in the pre-edge region, with an amplitude approximately 1.5 times that previously reported for the Co(III)–ethylenediamine system measured in axial geometry, corresponding to an estimated threefold enhancement under equivalent axial conditions. At the Cr K-edge, a clear, reproducible and well-resolved enantiomer-dependent XNCD response, featuring several distinct dichroic contributions, is observed, despite its lower amplitude relative to the Co analogue. To the best of our knowledge, this constitutes the first clear experimental observation of XNCD at the Cr K-edge. The distinct XNCD responses of these structurally related Cr(III) and Co(III) complexes demonstrate the sensitivity of K-edge XNCD to differences in the local chiral electronic environment of transition-metal centers.
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BibTeX
@misc{kordestani2026probing,
title = {{Probing Molecular Chirality from Vibrational to X-ray Energies in Cr(III) and Co(III) Complexes}},
author = {Nazanin Kordestani and Alessandro De Frenza and Thierry Buffeteau and Yann Danten and Nicolas Daugey and Patrick Rosa and Marie-Anne Arrio and Amélie Juhin and Nathan Yutronkie and Fabrice Wilhelm and Andrei Rogalev and Philippe Sainctavit and Elizabeth A. Hillard},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010596/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010596/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Probing Molecular Chirality from Vibrational to X-ray Energies in Cr(III) and Co(III) Complexes
AU - Nazanin Kordestani
AU - Alessandro De Frenza
AU - Thierry Buffeteau
AU - Yann Danten
AU - Nicolas Daugey
AU - Patrick Rosa
AU - Marie-Anne Arrio
AU - Amélie Juhin
AU - Nathan Yutronkie
AU - Fabrice Wilhelm
AU - Andrei Rogalev
AU - Philippe Sainctavit
AU - Elizabeth A. Hillard
PY - 2026
DA - 2026/10/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010596/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010596/v1
AB - The expression of molecular chirality across widely separated energy regimes was investigated in enantiomeric Cr(III) and Co(III) tris(trans-1,2-cyclohexanediamine) complexes using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and X-ray natural circular dichroism (XNCD), supported by single-crystal X-ray diffraction and density functional theory (DFT). Crystallographic analysis establishes the Λ-δδδ/lel3 and Δ-λλλ/lel3 configurations in the solid state, while the ECD spectra and comparison of experimental and DFT-calculated VCD spectra support retention of the lel3 stereochemical arrangement in solution. At the Co K-edge, pronounced opposite-sign XNCD responses are observed in the pre-edge region, with an amplitude approximately 1.5 times that previously reported for the Co(III)–ethylenediamine system measured in axial geometry, corresponding to an estimated threefold enhancement under equivalent axial conditions. At the Cr K-edge, a clear, reproducible and well-resolved enantiomer-dependent XNCD response, featuring several distinct dichroic contributions, is observed, despite its lower amplitude relative to the Co analogue. To the best of our knowledge, this constitutes the first clear experimental observation of XNCD at the Cr K-edge. The distinct XNCD responses of these structurally related Cr(III) and Co(III) complexes demonstrate the sensitivity of K-edge XNCD to differences in the local chiral electronic environment of transition-metal centers.
ER -