Ben Davis Group
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bendavisgroup.bsky.social
Ben Davis Group
@bendavisgroup.bsky.social
Chemical Biology at the University of Oxford and the Rosalind Franklin Institute
"There is hope in honest error."
bendavis.group
http://orcid.org/0000-0002-5056-407X
https://scholar.google.co.uk/citations?hl=en&user=llfD9gsAAAAJ
Mapping Vibronic Dynamics of Ultrafast Intersystem Crossing in an Earth-Abundant Ligand-Field Excited Complex
Intersystem crossing (ISC) is a central nonradiative pathway in transition-metal complexes, critically shaping their behavior in photocatalysis and optoelectronics. In 3d metal systems, ligand-field (LF, d–d) excited states are especially important, yet the mechanisms governing their ISC remain obscure because LF transitions are commonly masked by intense metal-to-ligand charge-transfer (MLCT) bands. This knowledge gap is significant, as LF states frequently participate in deactivation channels and directly influence the photochemical reactivity. Here, we focus on unraveling the ultrafast ISC dynamics in a carefully chosen model system with a simplified electronic structure: cobalt(III)-acetylacetonate, ([Co(acac)3]), a d6 low-spin complex. Upon selective 1A1 → 1T1 ligand-field excitation promoting a t2g → eg * electron, heterodyne-detected transient grating measurements with ∼10 fs pulses reveal vibrational coherences decaying in ∼50 fs, matching ISC dynamics. Fourier analysis reveals both low- and high-frequency vibrational modes associated with Co–O stretching and Co–O–C bending that actively mediate the spin-state transition. Complementary two-dimensional electronic spectroscopy (2DES) disentangles overlapping signals and localizes vibrational activity near the 1T1 excited-state absorption. Density functional theory (DFT) and GPU-accelerated hierarchy equation of motion (HEOM) calculations confirm that vibronic coupling, in concert with spin–orbit coupling (SOC), enables rapid singlet-to-triplet conversion via dynamic modulation of excited-state energies and reorganization along key nuclear coordinates. These results reveal that following LF excitation vibronic coupling plays an important role in reshaping excited-state potential energy surfaces and facilitating ISC in systems where SOC alone is weak. This work establishes a mechanistic foundation for understanding and controlling excited-state pathways in LF-dominated 3d transition-metal complexes.
pubs.acs.org
December 27, 2025 at 12:28 PM
November 5, 2025 at 8:49 PM
BGD has been awarded the ICS's Barry Cohen Award for Excellence in Medicinal Chemistry for 2025. www.chemistry.org.il/prizes-page/...
August 6, 2025 at 3:04 PM
Addressing NHS chemistry: Efficient quenching of excess TMT reagent and reversing TMT-over labelling in proteomic samples by methylamine, Mol Cell Proteomics, 2025, 24(4), 100948, doi.org/10.1016/j.mc...
April 8, 2025 at 8:26 AM
BGD has been awarded the ACS's Hudson Award for 2025. acscarb.org/awards/hudso...
March 31, 2025 at 3:26 PM
Isostere 18F-protein post-translational editing enables dynamic tracking of neurodegeneration biomarkers, bioRxiv 2025.01.26.634877; doi: doi.org/10.1101/2025...
Isostere 18F-protein post-translational editing enables dynamic tracking of neurodegeneration biomarkers
The neurofilament light chain protein (NfL) is a suggested general marker for neuronal loss. Its release from brain parenchyma into cerebral spinal fluid, and presumed detection in blood has seen it e...
doi.org
March 1, 2025 at 3:16 PM
Lipid-Modulated, Graduated Inhibition of N-Glycosylation Pathway Priming Suggests Wide Tolerance of ER Proteostasis to Stress, ACS Cent. Sci., 2025, 11, 107-115, doi.org/10.1021/acsc...
Lipid-Modulated, Graduated Inhibition of N-Glycosylation Pathway Priming Suggests Wide Tolerance of ER Proteostasis to Stress
Protein N-glycosylation is a cotranslational modification that takes place in the endoplasmic reticulum (ER). Disruption of this process can result in accumulation of misfolded proteins, known as ER s...
doi.org
March 1, 2025 at 3:13 PM
Structure of WzxE the Lipid III Flippase for Enterobacterial Common Antigen Polysaccharide, Open. Biol., 2025, 15, 240310, doi.org/10.1098/rsob...
Structure of WzxE the lipid III flippase for Enterobacterial Common Antigen polysaccharide | Open Biology
The enterobacterial common antigen (ECA) is conserved in Gram-negative bacteria of the Enterobacterales order although its function is debated. ECA biogenesis depends on the Wzx/Wzy-dependent strategy...
doi.org
March 1, 2025 at 3:12 PM
Start with some...Thoughts for the Future, Nature Chemical Biology, 2025, 21, 6-15; doi.org/10.1038/s415...
March 1, 2025 at 3:09 PM