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Updated: Sep 25, 2025

Sample Preparation for Probe Electrospray Ionization Mass Spectrometry
Published on: February 19, 2020
A "one pot" mass spectrometry technique for characterizing solution- and gas-phase photochemical reactions by
Rosaria Cercola1, Natalie G K Wong1, Chris Rhodes1
1Department of Chemistry, University of York Heslington York YO10 5DD UK caroline.dessent@york.ac.uk.
Abstract:
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 characterise both solution-phase and gas-phase photochemical reactions through electrospray ionisation 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 at 3.4 eV. The advantages of performing the gas-phase and solution-phase photochemical characterisations in a single instrument are discussed.
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