Artículo
Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy
Schüren, Andreas Oskar
; Ridgway, Benjamin Marc
; Di Salvo, Florencia
; Carella, Luca M.; Gramm, Verena K.; Metzger, Elisa; Doctorovich, Fabio
; Rentschler, Eva; Schünemann, Volker; Ruschewitz, Uwe; Klein, Axel
Fecha de publicación:
12/2022
Editorial:
Royal Society of Chemistry
Revista:
Dalton Transactions
ISSN:
1477-9226
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Iron sulphur halide clusters [Fe4S4Br4]2− and [Fe4S4X2Y2]2− (X, Y = Cl, Br, I) were obtained in excellent yields (77 to 78%) and purity from [Fe(CO)5], elemental sulphur, I2 and benzyltrimethylammonium (BTMA+) iodide, bromide and chloride. Single crystals of (BTMA)2[Fe4S4Br4] (1), (BTMA)2[Fe4S4Br2Cl2] (2), (BTMA)2[Fe4S4Cl2I2] (3), and (BTMA)2[Fe4S4Br2I2] (4) were isostructural to the previously reported (BTMA)2[Fe4S4I4] (5) (monoclinic, Cc). Instead of the chloride cubane cluster [Fe4S4Cl4]2−, we found the prismane-shaped cluster (BTMA)3[Fe6S6Cl6] (6) (P1̄). 57Fe Mössbauer spectroscopy indicates complete delocalisation with Fe2.5+ oxidation states for all iron atoms. Magnetic measurements showed small χMT values at 298 K ranging from 1.12 to 1.54 cm3 K mol−1, indicating the dominant antiferromagnetic exchange interactions. With decreasing temperature, the χMT values decreased to reach a plateau at around 100 K. From about 20 K, the values drop significantly. Fitting the data in the Heisenberg-Dirac-van Vleck (HDvV) as well as the Heisenberg Double Exchange (HDE) formalism confirmed the delocalisation and antiferromagnetic coupling assumed from Mössbauer spectroscopy.
Palabras clave:
IRON HALIDE-CLUSTERS
,
SINGLE CRYSTAL XRD
,
MOSSBAUER
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Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Citación
Schüren, Andreas Oskar; Ridgway, Benjamin Marc; Di Salvo, Florencia; Carella, Luca M.; Gramm, Verena K.; et al.; Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy; Royal Society of Chemistry; Dalton Transactions; 52; 5; 12-2022; 1277-1290
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