Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy

Schueren AO, Ridgway BM, Di Salvo F, Carella LM, Gramm VK, Metzger E, Doctorovich F, Rentschler E, Schuenemann V, Ruschewitz U, Klein A (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Dalton Transactions Royal Society of Chemistry

Book Volume: 52

Pages Range: 1277-1290

Journal Issue: 5

DOI: 10.1039/d2dt03203a

Abstract

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.

Involved external institutions

Universität zu Köln DE Germany (DE) Universidad de Buenos Aires (UBA) / University of Buenos Aires AR Argentina (AR) Johannes Gutenberg-Universität Mainz (JGU) DE Germany (DE) Technische Universität Kaiserslautern DE Germany (DE)

How to cite

APA:

Schueren, A.O., Ridgway, B.M., Di Salvo, F., Carella, L.M., Gramm, V.K., Metzger, E.,... Klein, A. (2022). Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy. Dalton Transactions, 52(5), 1277-1290. https://dx.doi.org/10.1039/d2dt03203a

MLA:

Schueren, Andreas O., et al. "Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy." Dalton Transactions 52.5 (2022): 1277-1290.

BibTeX: Download