Unique Hydration/Dehydration-Induced Vapochromic Behavior of a Charge-Transfer Salt Comprising Viologen and Hexacyanidoferrate(II)
We successfully prepared and crystallographically characterized the first intermolecular charge-transfer (CT)-based vapochromic compound, (EV)(H3O)2[Fe(CN)6] (1-Wet, EV2+: 1,1'-diethyl-4,4'-bipyridine-1,1'-diium), an ethyl viologen-containing CT salt. 1-Wet, which is purple in color, is transformed into a brown powder (1-Dry) upon exposure to methanol vapor, drying over silica gel, or heating; 1-Dry returns to 1-Wet upon exposure to water vapor. These color changes are induced by hydration and dehydration, and gravimetric analyses suggest that 1-Dry is the dehydrated form of 1-Wet, namely, (EV)(H)2[Fe(CN)6]. Interestingly, desorption of water molecules from the oxonium ions in 1-Wet produces isolated protons (H+) that remain in 1-Dry as counter cations. Powder X-ray crystal structure analysis of 1-Dry reveals the presence of very short contacts between the nitrogen atoms of adjacent [Fe(CN)6]4- anions in the crystal. The isolated protons are trapped between the nitrogen atoms of cyanido ligands to form very short N···H···N hydrogen bonds. A detailed comparison of the crystal structures of 1-Wet and 1-Dry reveals that hydration and dehydration induce changes in crystal packing and intermolecular CT interactions, resulting in reversible color changes.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2018 |
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| Erschienen: |
2018 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:57 |
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| Enthalten in: |
Inorganic chemistry - 57(2018), 4 vom: 19. Feb., Seite 2209-2217 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Tanaka, Rikako [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 07.03.2018 Date Revised 07.03.2018 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.7b03100 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM280721633 |
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| 100 | 1 | |a Tanaka, Rikako |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Unique Hydration/Dehydration-Induced Vapochromic Behavior of a Charge-Transfer Salt Comprising Viologen and Hexacyanidoferrate(II) |
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| 500 | |a Date Completed 07.03.2018 | ||
| 500 | |a Date Revised 07.03.2018 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a We successfully prepared and crystallographically characterized the first intermolecular charge-transfer (CT)-based vapochromic compound, (EV)(H3O)2[Fe(CN)6] (1-Wet, EV2+: 1,1'-diethyl-4,4'-bipyridine-1,1'-diium), an ethyl viologen-containing CT salt. 1-Wet, which is purple in color, is transformed into a brown powder (1-Dry) upon exposure to methanol vapor, drying over silica gel, or heating; 1-Dry returns to 1-Wet upon exposure to water vapor. These color changes are induced by hydration and dehydration, and gravimetric analyses suggest that 1-Dry is the dehydrated form of 1-Wet, namely, (EV)(H)2[Fe(CN)6]. Interestingly, desorption of water molecules from the oxonium ions in 1-Wet produces isolated protons (H+) that remain in 1-Dry as counter cations. Powder X-ray crystal structure analysis of 1-Dry reveals the presence of very short contacts between the nitrogen atoms of adjacent [Fe(CN)6]4- anions in the crystal. The isolated protons are trapped between the nitrogen atoms of cyanido ligands to form very short N···H···N hydrogen bonds. A detailed comparison of the crystal structures of 1-Wet and 1-Dry reveals that hydration and dehydration induce changes in crystal packing and intermolecular CT interactions, resulting in reversible color changes | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Okazawa, Atsushi |e verfasserin |4 aut | |
| 700 | 1 | |a Konaka, Hisashi |e verfasserin |4 aut | |
| 700 | 1 | |a Sasaki, Akito |e verfasserin |4 aut | |
| 700 | 1 | |a Kojima, Norimichi |e verfasserin |4 aut | |
| 700 | 1 | |a Matsushita, Nobuyuki |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d 1966 |g 57(2018), 4 vom: 19. Feb., Seite 2209-2217 |w (DE-627)NLM110650298 |x 1520-510X |7 nnns |
| 773 | 1 | 8 | |g volume:57 |g year:2018 |g number:4 |g day:19 |g month:02 |g pages:2209-2217 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.7b03100 |3 Volltext |
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