| Autor: |
Schüren, Andreas O., Ridgway, Benjamin M., Di Salvo, Florencia, Carella, Luca M., Gramm, Verena K., Metzger, Elisa, Doctorovich, Fabio, Rentschler, Eva, Schünemann, Volker, Ruschewitz, Uwe, Klein, Axel |
| Předmět: |
|
| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 2/7/2023, Vol. 52 Issue 5, p1277-1290, 14p |
| Abstrakt: |
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) (P1¯). 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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
|
