Magnetospectroscopic Studies of a Series of Fe(II) Scorpionate Complexes: Assessing the Relationship between Halide Identity and Zero-Field Splitting
Daniel J. SantaLucia, Laxmi Devkota, Sergey V. Lindeman, Andrew Ozarowski, J. Krzystek, Mykhaylo Ozerov, Samuel M. Greer, Daniel C. Cummins, Klaus H. Theopold, Mihail Atanasov, Joshua Telser, Adam T. Fiedler
TL;DR
This study explores how different halides affect the magnetic properties of iron complexes using advanced spectroscopic and theoretical methods.
Contribution
The paper provides a detailed electronic-structure analysis of Fe(II) scorpionate complexes with varying halides using advanced experimental and theoretical tools.
Findings
Halide identity significantly influences zero-field splitting in Fe(II) complexes.
Jahn–Teller distortions reduce symmetry in both solution and solid states.
Zero-field splitting arises from combined Jahn–Teller and ligand field effects, not spin–orbit coupling.
Abstract
Ferrous ions in four-coordinate environments are common in protein structures, synthetic catalysts, and molecular magnets. The 3d 6 configuration of high-spin Fe(II) imparts an S = 2 ground state, whose analysis using conventional spectroscopic methods is often hindered by substantial zero-field splitting (ZFS). Herein, we provide detailed electronic-structure descriptions for [FeIIX(Tp tBu,Me)] (1-X; X = F, Cl, Br, I), where (Tp tBu,Me)− is hydrotris(3-tert-butyl-5-methyl-pyrazol-1-yl)borate. The three pyrazolyl N-donors of the “scorpionate” ligand facially coordinate to Fe(II), giving idealized C 3v symmetry with the halide occupying the axial position. Although originally reported by Theopold and co-workers, this series is revisited herein using advanced experimental and theoretical tools. Ground-state transitions were probed by high-frequency and -field electron paramagnetic…
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Taxonomy
TopicsMagnetism in coordination complexes · Metal-Catalyzed Oxygenation Mechanisms · Metal complexes synthesis and properties