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Journal Article

Ultrafast primary processes of an iron-(III) azido complex in solution induced with 266 nm light

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Vennekate, H., Schwarzer, D., Torres-Alacan, J., Krahe, O., Filippou, A. C., Neese, F., et al. (2012). Ultrafast primary processes of an iron-(III) azido complex in solution induced with 266 nm light. Physical Chemistry Chemical Physics, 14(18), 6165-6172. doi:10.1039/C2CP23435A.

Cite as: http://hdl.handle.net/21.11116/0000-0007-E309-F
The ultrafast photo-induced primary processes of the iron-(III) azido complex, [FeIIIN3(cyclam-acetato)] PF6 (1), in acetonitrile solution at room temperature were studied using femtosecond spectroscopy with ultraviolet (UV) excitation and mid-infrared (MIR) detection. Following the absorption of a 266 nm photon, the complex undergoes an internal conversion back to the electronic doublet ground state at a time scale below 2 ps. Subsequently, the electronic ground state vibrationally cools with a characteristic time constant of 13 ps. A homolytic bond cleavage was also observed by the appearance of ground state azide radicals, which were identified by their asymmetric stretching vibration at 1659 cm−1. The azide radical recombines in a geminate fashion with the iron containing fragment within 20 ps. The cage escape leading to well separated fragments after homolytic Fe–N bond breakage was found to occur with a quantum yield of 35%. Finally, non-geminate recombination at nanosecond time scales was seen to further reduce the photolytic quantum yield to below 20% at a wavelength of 266 nm.