Foretić, Blaženka; Klaser, Teodoro; Ovčar, Juraj; Lončarić, Ivor; Žilić, Dijana; Šantić, Ana; Štefanić, Zoran; Bjelopetrović, Alen; Popović, Jasminka; Picek, Igor (2024) The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions. Molecules, 29 (23). ISSN 1420-3049
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Abstract
The structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting N-benzylyridinium-4-oxime cation (BPA4+) and electron donating hexacyanoferrate (II) are reported. The study of reversible stimuli-induced transformation between hydrated reddish-brown (BPA4)4[Fe(CN)6]·10H2O and anhydrous blue (BPA4)4[Fe(CN)6] revealed the origin of observed hydrochromic behavior. The comparison of the crystal structures of decahydrate and anhydrous phase showed that subsequent exclusion/inclusion of lattice water molecules induces structural relocation of one BPA4+ that alter the donor-to-acceptor charge-transfer states, resulting in chromotropism seen as reversible reddish-brown to blue color changes. The decreased donor-acceptor distance in (BPA4)4[Fe(CN)6] enhanced charge-transfer interaction allowing charge separation via one-electron transfer, as evidenced by in-situ ESR and FTIR spectroscopies. The reversibility of hydrochromic behavior was demonstrated by in-situ HT-XRPD, hot-stage microscopic and in situ diffuse-reflectance spectroscopic analyses. The insight into electronic structural features was obtained with density functional theory calculations, employed to elucidate electronic structure for both compounds. The electrical properties of the phases during dehydration process were investigated by temperature-dependent impedance spectroscopy.
| Item Type: | Article | ||||||||
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| Uncontrolled Keywords: | pyridinium oxime; hexacyanoferrate (II); charge-transfer complexes; charge separation; supramolecular complexes; electron transfer | ||||||||
| Subjects: | NATURAL SCIENCES > Chemistry BIOMEDICINE AND HEALTHCARE BIOMEDICINE AND HEALTHCARE > Basic Medical Sciences BIOMEDICINE AND HEALTHCARE > Pharmacy > Medical Biochemistry |
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| Divisions: | Division of Materials Chemistry Division of Materials Physics Division of Physical Chemistry Theoretical Physics Division |
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| Depositing User: | Ivana Vuglec | ||||||||
| Date Deposited: | 19 Sep 2025 10:52 | ||||||||
| URI: | http://fulir.irb.hr/id/eprint/9971 | ||||||||
| DOI: | 10.3390/molecules29235611 |
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