A “one pot” mass spectrometry technique for characterizing solution- and gas-phase photochemical reactions by electrospray mass spectrometry

The characterization of new photochemical pathways is important to progress the understanding of emerging areas of light-triggered inorganic and organic chemistry. In this context, the development of platforms to perform routine characterization of photochemical reactions remains an important goal for photochemists. Here, we demonstrate a new instrument that can be used to characterize both solution-phase and gas-phase photochemical reactions through electrospray ionization mass spectrometry (ESI-MS). The gas-phase photochemistry is studied by novel laser‐interfaced mass spectrometry (LIMS), where the molecular species of interest is introduced to the gas-phase by ESI, mass-selected and then subjected to laser photodissociation in the ion-trap. On-line solution-phase photochemistry is initiated by LEDs prior to ESI-MS in the same instrument with ESI-MS again being used to monitor photoproducts. Two ruthenium metal carbonyls, [Ru(η5-C5H5)(PPh3)2CO ][PF6] and [Ru(η5-C5H5)(dppe)CO][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane) are studied using this methodology. We show that the gas-phase photofragmentation pathways observed for the ruthenium complexes via LIMS (i.e. loss of CO + PPh3 ligands from Ru(η5-C5H5)(PPh3)2CO ]+ and loss of just CO from [Ru(η5-C5H5)(dppe)CO]+, mirror the solution-phase photochemistry. The advantages of performing the gas-phase and solution-phase photochemical characterizations in a single instrument are discussed.