Spin Crossover and Fluorine‐Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails

In coordination chemistry and materials science, terpyridine ligands are of great interest, due to their ability to form stable complexes with a broad range of transition metal ions. We report three terpyridine ligands containing different perfluorocarbon (PFC) tails on the backbone and the correspo...

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Veröffentlicht in:Chemistry : a European journal Jg. 29; H. 46; S. e202301246 - n/a
Hauptverfasser: Nößler, Maite, Neuman, Nicolás I., Böser, Lisa, Jäger, René, Singha Hazari, Arijit, Hunger, David, Pan, Yixian, Lücke, Clemens, Bens, Tobias, Slageren, Joris, Sarkar, Biprajit
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Germany Wiley Subscription Services, Inc 15.08.2023
Schlagworte:
Acetonitrile
Ambient temperature
Chemistry
cobalt
Coordination compounds
Crossovers
Electrochemical analysis
Electrochemistry
EPR spectroscopy
Fluorine
fluorine-specific interactions
Investigations
Ligands
Materials science
Metal complexes
Metal ions
Octanol
Oxidation
Perfluorocarbons
polyfluorocarbon
Spectra
Spectroscopy
Spin transition
Spin transitions
Tails
terpyridine
Transition metals
fluorine-specific interactions
cobalt
terpyridine
EPR spectroscopy
polyfluorocarbon
ISSN:0947-6539, 1521-3765, 1521-3765
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Zusammenfassung:In coordination chemistry and materials science, terpyridine ligands are of great interest, due to their ability to form stable complexes with a broad range of transition metal ions. We report three terpyridine ligands containing different perfluorocarbon (PFC) tails on the backbone and the corresponding FeII and CoII complexes. The CoII complexes display spin crossover close to ambient temperature, and the nature of this spin transition is influenced by the length of the PFC tail on the ligand backbone. The electrochemical properties of the metal complexes were investigated with cyclic voltammetry revealing one oxidation and several reduction processes. The fluorine‐specific interactions were investigated by EPR measurements. Analysis of the EPR spectra of the complexes as microcrystalline powders and in solution reveals exchange‐narrowed spectra without resolved hyperfine splittings arising from the 59Co nucleus; this suggests complex aggregation in solution mediated by interactions of the PFC tails. Interestingly, addition of perfluoro‐octanol in different ratios to the acetonitrile solution of the sample resulted in the disruption of the F ⋯ ${\cdots }$ F interactions of the tails. To the best of our knowledge, this is the first investigation of fluorine‐specific interactions in metal complexes through EPR spectroscopy, as exemplified by exchange narrowing. Iron(II) and cobalt(II) complexes with terpyridine ligands containing PFC tails are reported. All complexes are redox rich. The cobalt(II) complexes display spin crossover, and the magnetic properties in those cases are dependent on the length of the PFC tail. Fluorine‐specific interactions are observed between the PFC tails, and this effect translates into exchange narrowing of the corresponding EPR spectra of the cobalt complexes.
Bibliographie:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202301246