On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation
NiO-based nanomaterials have attracted considerable interest for different applications, which have stimulated the implementation of various synthetic approaches aimed at modulating their chemico-physical properties. In this regard, their bottom-up preparation starting from suitable precursors plays...
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| Format: | Article |
| Language: | English |
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MDPI AG
2024-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/29/3/642 |
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| author | Cristiano Invernizzi Gloria Tabacchi Roberta Seraglia Mattia Benedet Marco Roverso Chiara Maccato Sara Bogialli Davide Barreca Ettore Fois |
| author_facet | Cristiano Invernizzi Gloria Tabacchi Roberta Seraglia Mattia Benedet Marco Roverso Chiara Maccato Sara Bogialli Davide Barreca Ettore Fois |
| author_sort | Cristiano Invernizzi |
| collection | DOAJ |
| description | NiO-based nanomaterials have attracted considerable interest for different applications, which have stimulated the implementation of various synthetic approaches aimed at modulating their chemico-physical properties. In this regard, their bottom-up preparation starting from suitable precursors plays an important role, although a molecular-level insight into their reactivity remains an open issue to be properly tackled. In the present study, we focused on the fragmentation of Ni(II) diketonate-diamine adducts, of interest as vapor-phase precursors for Ni(II) oxide systems, by combining electrospray ionization mass spectrometry (ESI-MS) with multiple collisional experiments (ESI-MS<sup>n</sup>) and theoretical calculations. The outcomes of this investigation revealed common features in the fragmentation pattern of the target compounds: (i) in the first fragmentation, the three complexes yield analogous base-peak cations by losing a negatively charged diketonate moiety; in these cations, Ni-O and Ni-N interactions are stronger and the Ni positive charge is lower than in the parent neutral complexes; (ii) the tendency of ligand electronic charge to migrate towards Ni further increases in the subsequent fragmentation, leading to the formation of a tetracoordinated Ni environment featuring an interesting cation-π intramolecular interaction. |
| first_indexed | 2024-03-08T03:51:40Z |
| format | Article |
| id | doaj.art-5845693ff89a4246aaee2a894d094309 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T03:51:40Z |
| publishDate | 2024-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5845693ff89a4246aaee2a894d0943092024-02-09T15:18:56ZengMDPI AGMolecules1420-30492024-01-0129364210.3390/molecules29030642On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental InvestigationCristiano Invernizzi0Gloria Tabacchi1Roberta Seraglia2Mattia Benedet3Marco Roverso4Chiara Maccato5Sara Bogialli6Davide Barreca7Ettore Fois8Department of Science and High Technology, Insubria University and INSTM, 22100 Como, ItalyDepartment of Science and High Technology, Insubria University and INSTM, 22100 Como, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyCNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, ItalyDepartment of Science and High Technology, Insubria University and INSTM, 22100 Como, ItalyNiO-based nanomaterials have attracted considerable interest for different applications, which have stimulated the implementation of various synthetic approaches aimed at modulating their chemico-physical properties. In this regard, their bottom-up preparation starting from suitable precursors plays an important role, although a molecular-level insight into their reactivity remains an open issue to be properly tackled. In the present study, we focused on the fragmentation of Ni(II) diketonate-diamine adducts, of interest as vapor-phase precursors for Ni(II) oxide systems, by combining electrospray ionization mass spectrometry (ESI-MS) with multiple collisional experiments (ESI-MS<sup>n</sup>) and theoretical calculations. The outcomes of this investigation revealed common features in the fragmentation pattern of the target compounds: (i) in the first fragmentation, the three complexes yield analogous base-peak cations by losing a negatively charged diketonate moiety; in these cations, Ni-O and Ni-N interactions are stronger and the Ni positive charge is lower than in the parent neutral complexes; (ii) the tendency of ligand electronic charge to migrate towards Ni further increases in the subsequent fragmentation, leading to the formation of a tetracoordinated Ni environment featuring an interesting cation-π intramolecular interaction.https://www.mdpi.com/1420-3049/29/3/642transition metal complexesoxide nanomaterialsNiOmolecular precursorschemical vapor depositiondensity functional theory |
| spellingShingle | Cristiano Invernizzi Gloria Tabacchi Roberta Seraglia Mattia Benedet Marco Roverso Chiara Maccato Sara Bogialli Davide Barreca Ettore Fois On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation Molecules transition metal complexes oxide nanomaterials NiO molecular precursors chemical vapor deposition density functional theory |
| title | On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation |
| title_full | On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation |
| title_fullStr | On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation |
| title_full_unstemmed | On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation |
| title_short | On the Fragmentation of Ni(II) β-Diketonate-Diamine Complexes as Molecular Precursors for NiO Films: A Theoretical and Experimental Investigation |
| title_sort | on the fragmentation of ni ii β diketonate diamine complexes as molecular precursors for nio films a theoretical and experimental investigation |
| topic | transition metal complexes oxide nanomaterials NiO molecular precursors chemical vapor deposition density functional theory |
| url | https://www.mdpi.com/1420-3049/29/3/642 |
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