NOTICE: Due to a lapse in annual appropriations, most of this website is not being updated. Learn more.
Form submissions will still be accepted but will not receive responses at this time. Sections of this site for programs using non-appropriated funds (such as NVLAP) or those that are excepted from the shutdown (such as CHIPS and NVD) will continue to be updated.
An official website of the United States government
Here’s how you know
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
Secure .gov websites use HTTPS
A lock (
) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.
Photodynamics of Asymmetric Di-Iron-Cyano Hydrogenases Examined by Time-Resolved Mid-Infrared Spectroscopy
Published
Author(s)
Edwin J. Heilweil, Amber Meyers, Christopher J. Stromberg
Abstract
Two anionic asymmetric Fe-Fe Hydrogenase model compounds containing a single CN and five CO ligands: [Fe2(μ-S2C3H6)(CO)5(CN)1]1− (1) and [Fe2(μ-S2C2H4)(CO)5(CN)1]1− (2) dissolved in room temperature acetonitrile are examined. The molecular asymmetry affects the redox potentials of the central iron atoms thus changing the catalytic properties of the compounds. Femtosecond ultraviolet excitation with mid-infrared probe spectroscopy was employed to better understand the ultrafast dynamics of the enzyme active site. Continuous ultraviolet lamp excitation with Fourier Transform infrared (FTIR) spectroscopy was also used to explore stable product formation on the second timescale. For both model compounds, two timescales are observed; a 20-30 ps decay and formation of a long-lived photoproduct. The picosecond decay is assigned to vibrational cooling and rotational dynamics while the residual spectra remains for up to 300 ps suggesting formation of new photoproducts. Static FTIR spectroscopy yielded a different stable photoproduct than observed on the ultrafast timescale. Density functional theory (DFT) calculations simulated photoproducts for CO-loss and CN-loss isomers and the resulting photoproduct spectra suggest the picosecond transients arise from a complex mixture of isomerization after CO-loss while dimerization and formation of a CN-containing Fe-CO-Fe bridged species are also considered.
Heilweil, E.
, Meyers, A.
and Stromberg, C.
(2021),
Photodynamics of Asymmetric Di-Iron-Cyano Hydrogenases Examined by Time-Resolved Mid-Infrared Spectroscopy, The Journal of Physical Chemistry A, [online], https://dx.doi.org/10.1021/acs.jpca.0c08921
(Accessed October 9, 2025)