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  • Review Article
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Molecular synthesis with gaseous fragment ions on surfaces

Nature Reviews Chemistry volume 9, pages 470–480 (2025)Cite this article

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Abstract

Chemists often treat gaseous fragment ions as esoteric chemical species of interest to only analytical mass spectrometry and gas-phase ion chemistry. However, their potential as building blocks for designing new compounds in the condensed phase is largely unexplored. Developments in preparative mass spectrometry instrumentation have opened up a new research field focused on understanding the chemistry of well-defined gaseous fragment ions on surfaces. In this Review, we highlight the preparative potential of gaseous fragment ions for synthesizing new compounds in the condensed phase. We discuss factors affecting the selectivity of the observed reactivity of fragment ions, examine the effect of charge on reaction mechanisms, and introduce the unexpected reactivity of ions of the same polarity on surfaces in the absence of solvent molecules. These developments hold the potential to transform preparative mass spectrometry into a valuable method for small-scale chemical synthesis in almost all fields of molecular sciences.

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Fig. 1: An ESI-based high-flux preparative mass spectrometer for fragment ion deposition.
Fig. 2: Generation and selected reactions of [B12X11]− (X = Cl, Br, and I) ions in the gas phase.
Fig. 3: An overview of the reactions of [B12X11]− and [B12I8(S)(CN)]− fragment ions on surfaces.
Fig. 4: Deposition of undercoordinated metal chalcogenide clusters and nanospray desorption electrospray ionization (nano-DESI) analysis of their reaction products on surfaces.
Fig. 5: Comparison of the optimized structures of [Ni(bpy)3]2+ with and without a stable counterion on a C–H-terminated interface.

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Acknowledgements

The authors acknowledge support from the Air Force Office of Scientific Research (AFOSR) under grant FA9550-23-1-0137 (H.Y.S-O, X.L., J.L.) and the Volkswagen Foundation for a Freigeist Fellowship (J.W.).

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Authors and Affiliations

  1. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Leipzig, Germany

    Jonas Warneke, Markus Rohdenburg & Harald Knorke

  2. Leibniz Institute of Surface Engineering (IOM), Leipzig, Germany

    Jonas Warneke

  3. James Tarpo Jr. and Margaret Tarpo Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Hugo Y. Samayoa-Oviedo, Xilai Li & Julia Laskin

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Contributions

J.L. and J.W. conceptualized the article and wrote major parts of the text. All authors researched literature for the article. J.W., M.R., H.K. and J.L. contributed substantially to discussion of the content. All authors contributed substantially to writing the article. All authors reviewed and/or edited the manuscript before submission.

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Correspondence to Julia Laskin.

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Warneke, J., Samayoa-Oviedo, H.Y., Rohdenburg, M. et al. Molecular synthesis with gaseous fragment ions on surfaces. Nat Rev Chem 9, 470–480 (2025). https://doi.org/10.1038/s41570-025-00719-1

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