Design and Performance of a Soft-Landing Instrument for Fragment Ion Deposition

We report the development of a new high-flux electrospray ionization-based instrument for soft landing of mass-selected fragment ions onto surfaces. Collision-induced dissociation is performed in a collision cell positioned after the dual electrodynamic ion funnel assembly. The high duty cycle of the instrument enables high-coverage deposition of mass-selected fragment ions onto surfaces at a defined kinetic energy. This capability facilitates the investigation of the reactivity of gaseous fragment ions in the condensed phase. We demonstrate that the observed reactions of deposited fragment ions are dependent on the structure of the ion and the composition of either ionic or neutral species codeposited onto a surface. The newly developed instrument provides access to high-purity ion fragments as building blocks for the preparation of unique ionic layers

Gas Phase Reactivity of [Mo₆X₁₄]^2– Dianions (X = Cl – I)

We investigate collision-induced dissociation (CID) of [Mo6X14]2– (X = Cl, Br, I) and the reactivity of fragment ions of these precursors with background gases. Ion mobility measurements and theoretical calculations provide structural information for some of the observed ions. Sequential losses of MoX2 units dominate the dissociation pathways of [Mo6Cl14]2–. Meanwhile, loss of X radicals is the main channel for X = Br and I. Ion mobility measurements and computational investigations indicate minor structural changes in the octahedral Mo6 unit for [Mo6Im]− (m = 6–13) fragments. We observe that mass spectra obtained using CID substantially vary among mass spectrometers: Specifically, ions with molecular formula [Mo6Xm(O2)n]− (X = Br and I) are observed as dominant species produced through reactions with O2 in several mass spectrometers, but also adduct free fragment ions were observed in other instruments, depending on the background conditions. Ion-trap fragmentation combined with theoretical investigations indicates that spontaneous losses of X radicals occur upon binding of O2 to [Mo6Im]− fragments (m ≤ 12). Theoretical investigations indicate that both oxygen atoms are bound to the vacant sites of the Mo6 units. This study opens up a new vista to generate and study a large variety of hexanuclear Mo6Xm(O2)n anions