Electrochromic Behavior of a Di-μ-Phenoxo-Bridged Iron(III) Salen-Based Complex: A Combined Electrochemical and Spectroelectrochemical Study.

A tetraphenylethylene-based salen-type Schiff base ligand and its Fe(III) coordination complex were synthesized and characterized using spectroscopic, electrochemical, mass spectrometric, and single-crystal X-ray diffraction techniques. The ligand features an N2O2 donor set and was obtained via Schiff base condensation with ethylenediamine, while reaction with FeCl3 afforded a di-μ-phenoxo-bridged dinuclear Fe(III) complex under mild conditions. Unlike previously reported Fe(III)-salen electrochromic systems, which are predominantly mononuclear and exhibit ligand-centered redox processes with limited modulation of intraligand electronic communication, the present system incorporates a rigid tetraphenylethylene scaffold and forms a centrosymmetric di-μ-phenoxo-bridged Fe(III) dimer. This structural motif enables coordination-induced electronic coupling between phenolate units, resulting in a distinct splitting of ligand-centered oxidation processes. Single-crystal X-ray diffraction confirmed a di-μ-phenoxo-bridged Fe(III) dimer with distorted octahedral geometry. Electrochemical studies show a quasi-reversible ligand-centered oxidation in the free ligand, which splits into two separate redox events upon complexation, indicating the emergence of electronically non-equivalent redox sites. Spectroelectrochemical analysis reveals the formation of phenoxyl radical species accompanied by ligand-centered intervalence charge-transfer transitions and the appearance of a near-infrared absorption band upon oxidation. A reversible color change from red to blue is observed, reflecting redox-driven modulation of the electronic structure. Overall, this work demonstrates that incorporation of a tetraphenylethylene-based salen framework and formation of a di-μ-phenoxo-bridged Fe(III) dimer enables coordination-triggered intraligand electronic communication, leading to fundamentally different redox behavior compared to previously reported Fe(III)-salen electrochromic complexes, while no reversible metal-centered redox processes were detected within the experimentally investigated potential window.