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J. Mol. Sci.","IJMS"],"abstract":"<jats:p>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-\u03bc-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-\u03bc-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-\u03bc-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\u2013transfer 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-\u03bc-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.<\/jats:p>","DOI":"10.3390\/ijms27156714","type":"journal-article","created":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T16:11:56Z","timestamp":1785168716000},"page":"6714","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Electrochromic Behavior of a Di-\u03bc-Phenoxo-Bridged Iron(III) Salen-Based Complex: A Combined Electrochemical and Spectroelectrochemical Study"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2794-4373","authenticated-orcid":false,"given":"Sergiusz","family":"Napiera\u0142a","sequence":"first","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mateusz","family":"Bogus\u0142awski","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7202-9169","authenticated-orcid":false,"given":"Maciej","family":"Kubicki","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0605-6078","authenticated-orcid":false,"given":"Monika","family":"Wa\u0142\u0119sa-Chorab","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,7,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"410","DOI":"10.1039\/B307853C","article-title":"Metal\u2013Salen Schiff Base Complexes in Catalysis: Practical Aspects","volume":"33","author":"Cozzi","year":"2004","journal-title":"Chem. 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