preprints.org > chemistry and materials science > theoretical chemistry > doi: 10.20944/preprints202312.1647.v1

Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Version 1 : Received: 21 December 2023 / Approved: 21 December 2023 / Online: 21 December 2023 (14:40:00 CET)

NiO-based nanomaterials have attracted a great deal of interest in view of various applications, that have stimulated the implementation of various synthetic approaches to control their chemico-physical properties as a function of the desired end-use. In this regard, their bottom-up preparation starting from suitable precursors plays an important role, but a molecular level in-sight into their reactivity remains an open challenge. In this study, we focus on the fragmentation of Ni(II) diketonate-diamine adducts, of interest as precursors for Ni(II) oxide systems, by com-bined electrospray ionization mass spectrometry (ESI-MS) with multiple collisional experiments (ESI-MSn) and theoretical calculations. The joint analyses revealed common features in the frag-mentation pattern of the target compounds: i) in the first-fragmentation, all three complexes form analogous base-peak cations by losing a negatively charged diketonate; in these cations, Ni-O and Ni-N interactions are stronger and the Ni positive charge is lower than in the neutral complexes; ii) the tendency of ligand electronic charge to migrate towards Ni further increases in the subsequent fragmentation processes, leading to the formation – in all three cases – of a tetracoordinated Ni environment involving an interesting cation-π intramolecular interaction.

transition metal complexes; oxide nanomaterials; NiO; molecular precursors; chemical vapor deposition; density functional theory; simulations

Chemistry and Materials Science, Theoretical Chemistry

* All users must log in before leaving a comment