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An Interplay Between Infrared Multiphoton Dissociation Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry and Density Functional Theory Computations in the Characterization of a Tripodal Quinolin-8-Olate Gd(III) Complex |
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| Authors: | Margherita De Bonis Giuliana Bianco Mario Amati Sandra Belviso Tommaso R I Cataldi Francesco Lelj | |
| Institution: | 1. LaMI, Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano, 10, 85100, Potenza, Italy 2. Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano, 10, 85100, Potenza, Italy 4. Centro Interdipartimentale CIGAS, Università degli Studi della Basilicata, Via dell’Ateneo Lucano, 10, 85100, Potenza, Italy 5. LaSCAMM, INSTM- Sezione Basilicata, Università degli Studi della Basilicata, Via dell’Ateneo Lucano, 10, 85100, Potenza, Italy 3. Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Campus Universitario, Via Orabona 4, 70126, Bari, Italy 6. Centro Interdipartimentale SMART, Università degli Studi di Bari Aldo Moro, Campus Universitario, Via E. Orabona 4, 70126, Bari, Italy |
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| Abstract: | A new hexadentate, tripodal 8-hydroxyquinoline based ligand (QH3) and its gadolinium(III) tris-chelated (GdQ) complex with hemicage structure was investigated by using high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICRMS). The protonated adduct of the free ligand and its hemicage tripodal Gd(III) complex, GdQ + H]+, were first observed in experiments of electrospray ionization (ESI) with a linear ion trap (LTQ) mass spectrometer and further investigated by using high resolution FTICRMS. Gas-phase dissociation of the protonated Gd(III) complex, by infrared multiphoton dissociation (IRMPD) FTICR MS, demonstrated a fragmentation pattern with six main product cluster ions labeled as Fn]+ (n?=?1 up to 6). These product ions suggest the elimination of 7-amino-alkyl or 7-alkyl chains of the hemicage moiety. High resolution MS conditions allowed the elucidation of the fragmentation pattern and product ion structures along with the determination, among the isotopic pattern of Gd, of the chemical compositions of closely related species, which differ in terms of hydrogen content. Among the Gd six naturally stable isotopes, 158Gd is the most abundant, and its peak within each cluster was used as a reference for distinguishing each product ions. Computational DFT investigations were applied to give support to some hypothesis of fragmentation pathways, which could not have been easily justified on the basis of the experimental work. Furthermore, computational studies suggested the coordination geometry of the protonated parent complex and the five- and four-coordinated complexes, which derive from its fragmentation. Furthermore, experimental and computational evidences were collected about the octet spin state of the parent compound.  | |
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