A Neutral Fe4tBuL4 All Ferric Grid Complex: Structural and Variable Temperature Magnetic Properties. Issue 8 (17th February 2020)

• Record Type: Journal Article
• Authors: Bonanno, Nico M.; Patrick, Brian O.; Seda, Takele; Lemaire, Martin T.
• Is Part Of: European journal of inorganic chemistry. Issue 8(2020)
• Page Start: 711
• Page End: 715
• Publication Date: 2020-02-17
• Subjects: Iron -- [2×2] Grid complexes -- Redox‐active ligands -- Magnetic properties -- Self‐assembly; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201901316
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : A neutral all ferric [2×2] grid complex Fe4 t Bu L4 1 was synthesized and characterized in the solid‐state by X‐ray crystallography, variable temperature magnetic susceptibility and Mössbauer spectroscopy. The absence of any coordinate bond or other structural changes between 90(2) and 320(2) K indicated no changes to the electronic structure of 1 occurred in the solid‐state over this temperature range. Variable temperature magnetic susceptibility data were fitted to an isotropic spin Hamiltonian model and suggested weak antiferromagnetic exchange coupling between the high‐spin ferric ions ( J = –16.1 cm ‐1 ). Mössbauer spectroscopy parameters ( δ = 0.416(9) mm s –1 & ΔEQ = 0.87(7) mm s ‐1 ), powder EPR spectra, and broken symmetry density functional theory calculations supported the high‐spin ferric oxidation state assignment. Abstract : We describe the structure, electrochemical and variable temperature magnetic properties of a neutral [2×2] all ferric grid complex with a previously reported ditopic redox‐active ligand. The four Fe ions are shown to be in high‐spin states at all temperatures with weak antiferromagnetic magnetic exchange interactions.