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Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

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Journal of The American Society for Mass Spectrometry

Abstract

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy n– and VxOyCln– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln– and VxOyCl(L)(n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1–2)– and VxOy (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

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Acknowledgments

This research was funded by the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy (DOE). N.M.A. acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI). G.E.J. acknowledges support from the Linus Pauling Fellowship and the Laboratory Directed Research and Development Program at the Pacific Northwest National Laboratory (PNNL). This work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the U.S. DOE.

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  1. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Naila M. Al Hasan, Grant E. Johnson & Julia Laskin

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  1. Naila M. Al Hasan
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Al Hasan, N.M., Johnson, G.E. & Laskin, J. Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation. J. Am. Soc. Mass Spectrom. 24, 1385–1395 (2013). https://doi.org/10.1007/s13361-013-0683-0

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