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A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe 3 (μ 3 ‐O) Triangle
Author(s) -
Govor Evgen V.,
AlAmeed Karrar,
Chakraborty Indranil,
Coste Carla S.,
Govor Olena,
Sanakis Yiannis,
McGrady John E.,
Raptis Raphael G.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201610534
Subject(s) - redox , electron paramagnetic resonance , oxidation state , crystallography , chemistry , cluster (spacecraft) , cascade , metal , spin states , density functional theory , bond length , electron , electron localization function , spin (aerodynamics) , inorganic chemistry , nuclear magnetic resonance , computational chemistry , crystal structure , physics , organic chemistry , chromatography , quantum mechanics , computer science , programming language , thermodynamics
One‐electron reduction of a pyrazolate‐bridged triangular Fe 3 (μ 3 ‐O) core induces a cascade wherein all three metal centers switch from high‐spin Fe 3+ to low‐spin Fe 2.66+ . This hypothesis is supported by spectroscopic data ( 1 H‐NMR, UV‐vis‐NIR, infra‐red, 57 Fe‐Mössbauer, EPR), X‐ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters. This is, to the best of our knowledge, the first example of a one‐electron redox event causing concerted change in multiple iron centers.