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...
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Veröffentlicht in: | Chemical communications (Cambridge, England) England), 2024-01, Vol.60 (95), p.14117-14120 |
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Format: | Artikel |
Sprache: | eng |
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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. |
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ISSN: | 1359-7345 1364-548X |
DOI: | 10.1039/d4cc05161k |