Magnetically stabilized Fe8(μ4-S)6S8 clusters in Ba6Fe25S27Electronic supplementary information (ESI) available: The crystallographic information file, Hückel parameters, and details of DFT calculations. See DOI: 10.1039/c4dt01182a

• Main Authors: Stacey, Timothy E, Borg, Christopher K. H, Zavalij, Peter J, Rodriguez, Efrain E
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c4dt01182a

We have prepared Ba 6 Fe 25 S 27 , and studied its magnetic properties and electronic structure. Single crystal diffraction revealed a cubic phase ( Pm 3&cmb.macr; m ) with a = 10.2057(9) Å and Z = 1. Within the large cubic cell, tetrahedrally coordinated Fe atoms arrange into octonuclear Fe 8 (μ 4 -S) 6 (S 8 ) clusters, which can be described as a cube of Fe atoms with six face-capping and eight terminal S atoms. SQUID magnetometry measurements reveal an antiferromagnetic transition at 25 K and anomalous high-temperature dependence of magnetic susceptibility that is non-Curie like-two magnetic signatures which mimic behavior seen in the parent phases of Fe-based superconductors. Using a combined DFT and molecular orbital based approach, we provide an interpretation of the bonding and stability within Ba 6 M 25 S 27 (M = Fe, Co, Ni) and related M 9 S 8 phases. Through a σ-bonding molecular orbital model of the transition metal coordination environments, we illustrate how the local stability can be enhanced through addition of Ba. In addition, we perform spin-polarized DFT calculations on Ba 6 Fe 25 S 27 to determine the effect of adopting an antiferromagnetic spin state on its electronic structure. By studying the magnetic properties from an empirical and computational perspective, we hope to elucidate what aspects of the magnetic structure are significant to bonding. We have prepared Ba 6 Fe 25 S 27 , and studied its magnetic properties and electronic structure. Using a combined DFT and molecular orbital based approach, we provide an interpretation of the bonding and stability within Ba 6 M 25 S 27 (M = Fe, Co, Ni) and related M9S8 phases.