Unique Hydration/Dehydration-Induced Vapochromic Behavior of a Charge-Transfer Salt Comprising Viologen and Hexacyanidoferrate(II)
| Autor: | Rikako Tanaka, Akito Sasaki, Atsushi Okazawa, Norimichi Kojima, Nobuyuki Matsushita, Hisashi Konaka |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Silica gel Salt (chemistry) 02 engineering and technology Crystal structure 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Inorganic Chemistry Crystal chemistry.chemical_compound Crystallography chemistry Desorption Gravimetric analysis Molecule Physical and Theoretical Chemistry 0210 nano-technology Oxonium ion |
| Zdroj: | Inorganic Chemistry. 57:2209-2217 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.7b03100 |
| Popis: | 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 ve... |
| Databáze: | OpenAIRE |
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