Pyrazolate-supported Cr3(μ3-O) cores; homovalent Cr3III and mixed-valent Cr2IIICrIV

The thermally assisted reaction of Cr(NO3)3·9H2O, 4-Cl-pzH, and Et3N yielded electrochemically active trinuclear CrIII–oxo–pyrazolate complexes with formula (Ph4P)2[Cr3(μ3-O)(μ-4-Cl-pz)6X3], X = Cl (1) and Br (2). Magnetic susceptibility measurements and EPR spectroscopy show that 1 has an antiferro...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemical communications (Cambridge, England) England), 2024-01, Vol.60 (95), p.14117-14120
Hauptverfasser: López-Plá, Jessica M, Obies, Mohammed, Zahariou, Georgia, Pissas, Michael, Sanakis, Yiannis, McGrady, John E, Raptis, Raphael G
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The thermally assisted reaction of Cr(NO3)3·9H2O, 4-Cl-pzH, and Et3N yielded electrochemically active trinuclear CrIII–oxo–pyrazolate complexes with formula (Ph4P)2[Cr3(μ3-O)(μ-4-Cl-pz)6X3], X = Cl (1) and Br (2). Magnetic susceptibility measurements and EPR spectroscopy show that 1 has an antiferromagnetically coupled Cr3O-core with an S = 1/2 ground state and isotropic exchange of J = −12.7 cm−1. (Hex = −2JS1S2). Cyclic voltammetry reveals a facile reversible oxidation to the formally Cr2IIICrIV analogue of 1. The UV-Vis-NIR spectra of Cr3III and Cr2IIICrIV species have been assigned with the help of DFT calculations.
ISSN:1359-7345
1364-548X
DOI:10.1039/d4cc05161k