The formation of W x O y+●/-● clusters in the gas phase was studied by laser desorption ionization (LDI) and matrix assisted laser desorption ionization (MALDI) of solid WO3. LDI produced (WO3) n+ ●/- ● (n = 1-7) clusters. In MALDI, when using nano-diamonds (NDs), graphene oxide (GO), or fullerene (C60) matrices, higher mass clusters were generated. In addition to (WO3) n-● clusters, oxygen-rich or -deficient species were found in both LDI and MALDI (with the total number of clusters exceeding one hundred ≈ 137). This is the first time that such matrices have been used for the generation of(WO3) n+●/-● clusters in the gas phase, while new high mass clusters (WO3) n-● (n = 12-19) were also detected. Graphical Abstract.

Center for Syntheses at Sustainable Conditions and Their Management Faculty of Science Department of Chemistry Masaryk University Kamenice 5 A14 625 00 Brno Czech Republic

Department of Chemistry Faculty of Science Masaryk University Kamenice 5 A14 625 00 Brno Czech Republic

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