Unusual π–π interactions directed by the [{(C6H6)Ru}2W8O30(OH)2]6− hybrid anion
| Autor: | Maxim N. Sokolov, Vasily V. Kokovkin, Pavel A. Abramov, Alexander S. Novikov, Anna A. Mukhacheva, Vladislav Yu. Komarov |
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| Rok vydání: | 2021 |
| Předmět: |
Aqueous solution
010405 organic chemistry Chemistry Stacking Cationic polymerization Protonation General Chemistry Crystal structure 010402 general chemistry Condensed Matter Physics Electrochemistry 01 natural sciences 0104 chemical sciences Catalysis Crystallography General Materials Science Single crystal |
| Zdroj: | CrystEngComm. 23:4125-4135 |
| ISSN: | 1466-8033 |
| Popis: | The [{(C6H6)Ru}2W8O30(OH)2]6− hybrid (organometallic–POM) anion was used as a pH-tunable building block to create special conditions for realizing π–π interactions in the crystal structure. Changing the pH of an aqueous solution of Na6[{(C6H6)Ru}2W8O28(OH)2]·16H2O (1) results in isolation of a series of new compounds with different Na+/H+ ratios in the cationic composition: Na5.5H0.5[{(C6H6)Ru}2W8O28(OH)2]·15H2O (2), Na5H[{(C6H6)Ru}2W8O28(OH)2]·22H2O (3), Na4H2[{(C6H6)Ru}2W8O28(OH)2]·24H2O (4), Na3H3[{(C6H6)Ru}2W8O28(OH)2]·23H2O (5), and NaH5[{(C6H6)Ru}2W8O28(OH)2]·9H2O (6). All complexes were characterized by single crystal X-ray diffraction (SCXRD) analysis and ICP-AES. The presence of π–π stacking was detected for moderate-to-highly protonated 3–6. The energy of such interactions was calculated to increase in the following order: 6 (5.0 kJ mol−1) < 5 (7.6 kJ mol−1) < 3 (10.0 kJ mol−1). 1 was studied for its electrochemical behavior in 0.5 M Li2SO4 and as a paste electrode component in methanol. Catalytic activity in methanol oxidation was detected. |
| Databáze: | OpenAIRE |
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