Working Paper
Authors
- Niklas Gessner University of Regensburg ,
- Anna K. Bäck University of Vienna ,
- Johannes Knorr University of Erlangen-Nuremberg ,
- Christoph Nagel University of Würzburg ,
- Philipp Marquetand University of Vienna ,
- Ulrich Schatzschneider University of Würzburg ,
- Leticia González University of Vienna ,
- Patrick Nuernberger
University of Regensburg
Abstract
Transition metal complexes capable of releasing small-molecule messengers such as carbon monoxide and nitric oxide upon photoactivation are versatile tools in various fields of chemistry and biology. In this work, we report on the ultrafast photochemistry of [Mo(CO)2(NO)(iPr3tacn)]PF6 (iPr3tacn = 1,4,7-triisopropyl-1,4,7-triazacyclononane), which was synthesized and subsequently characterized in continuous illumination studies and with femtosecond UV-pump/UV-probe and UV-pump/MIR-probe spectroscopy, as well as with stationary calculations. The experimental and theoretical results demonstrate that while the photodissociation of one of the two CO ligands upon UV excitation can be inferred both on an ultrafast timescale as well as under exposure times of several minutes, no evidence of NO release is observed under the same conditions. The binding mode of the diatomic ligands is impacted by the electronic excitation, and excited molecules are observed on a timescale of tens of picoseconds before CO is released from the coordination sphere. Furthermore, based on calculated potential energy scans, we suggest that photolysis of NO could be possible after a subsequent excitation of an electronically excited state with a second laser pulse, or by accessing low-lying excited states that otherwise cannot be directly excited by light.
Content

Supplementary material

Supporting Information
Supplementary information on the potential photoproduct exploration, fitting of FTIR spectra, geometric features of the optimized geometry, full charge transfer characterization, and potential energy scan