The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions
The structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting <i>N</i>-benzylyridinium-4-oxime cation (BPA4<sup>+</sup>) and electron donating hexacyanoferrate (II) are reported. The study of...
Saved in:
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/29/23/5611 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1850261293743734784 |
|---|---|
| author | Blaženka Foretić Teodoro Klaser Juraj Ovčar Ivor Lončarić Dijana Žilić Ana Šantić Zoran Štefanić Alen Bjelopetrović Jasminka Popović Igor Picek |
| author_facet | Blaženka Foretić Teodoro Klaser Juraj Ovčar Ivor Lončarić Dijana Žilić Ana Šantić Zoran Štefanić Alen Bjelopetrović Jasminka Popović Igor Picek |
| author_sort | Blaženka Foretić |
| collection | DOAJ |
| description | The structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting <i>N</i>-benzylyridinium-4-oxime cation (BPA4<sup>+</sup>) and electron donating hexacyanoferrate (II) are reported. The study of reversible stimuli-induced transformation between hydrated reddish-brown (BPA4)<sub>4</sub>[Fe(CN)<sub>6</sub>]·10H<sub>2</sub>O and anhydrous blue (BPA4)<sub>4</sub>[Fe(CN)<sub>6</sub>] 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<sup>+</sup> 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)<sub>4</sub>[Fe(CN)<sub>6</sub>] 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. |
| format | Article |
| id | doaj-art-5fd946c240434ff9b2f596db7c7d86c3 |
| institution | OA Journals |
| issn | 1420-3049 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-5fd946c240434ff9b2f596db7c7d86c32025-08-20T01:55:27ZengMDPI AGMolecules1420-30492024-11-012923561110.3390/molecules29235611The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) IonsBlaženka Foretić0Teodoro Klaser1Juraj Ovčar2Ivor Lončarić3Dijana Žilić4Ana Šantić5Zoran Štefanić6Alen Bjelopetrović7Jasminka Popović8Igor Picek9Department of Chemistry and Biochemistry, School of Medicine, University of Zagreb, Šalata 3, HR-10000 Zagreb, CroatiaPhysics Department, Faculty of Science, University of Zagreb, Bijenička cesta 32, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaDepartment of Chemistry and Biochemistry, School of Medicine, University of Zagreb, Šalata 3, HR-10000 Zagreb, CroatiaThe structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting <i>N</i>-benzylyridinium-4-oxime cation (BPA4<sup>+</sup>) and electron donating hexacyanoferrate (II) are reported. The study of reversible stimuli-induced transformation between hydrated reddish-brown (BPA4)<sub>4</sub>[Fe(CN)<sub>6</sub>]·10H<sub>2</sub>O and anhydrous blue (BPA4)<sub>4</sub>[Fe(CN)<sub>6</sub>] 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<sup>+</sup> 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)<sub>4</sub>[Fe(CN)<sub>6</sub>] 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.https://www.mdpi.com/1420-3049/29/23/5611pyridinium oximehexacyanoferrate (II)charge-transfer complexescharge separationsupramolecular complexeselectron transfer |
| spellingShingle | Blaženka Foretić Teodoro Klaser Juraj Ovčar Ivor Lončarić Dijana Žilić Ana Šantić Zoran Štefanić Alen Bjelopetrović Jasminka Popović Igor Picek The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions Molecules pyridinium oxime hexacyanoferrate (II) charge-transfer complexes charge separation supramolecular complexes electron transfer |
| title | The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions |
| title_full | The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions |
| title_fullStr | The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions |
| title_full_unstemmed | The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions |
| title_short | The Reversible Electron Transfer Within Stimuli-Responsive Hydrochromic Supramolecular Material Containing Pyridinium Oxime and Hexacyanoferrate (II) Ions |
| title_sort | reversible electron transfer within stimuli responsive hydrochromic supramolecular material containing pyridinium oxime and hexacyanoferrate ii ions |
| topic | pyridinium oxime hexacyanoferrate (II) charge-transfer complexes charge separation supramolecular complexes electron transfer |
| url | https://www.mdpi.com/1420-3049/29/23/5611 |
| work_keys_str_mv | AT blazenkaforetic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT teodoroklaser thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT jurajovcar thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT ivorloncaric thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT dijanazilic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT anasantic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT zoranstefanic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT alenbjelopetrovic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT jasminkapopovic thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT igorpicek thereversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT blazenkaforetic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT teodoroklaser reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT jurajovcar reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT ivorloncaric reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT dijanazilic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT anasantic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT zoranstefanic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT alenbjelopetrovic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT jasminkapopovic reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions AT igorpicek reversibleelectrontransferwithinstimuliresponsivehydrochromicsupramolecularmaterialcontainingpyridiniumoximeandhexacyanoferrateiiions |