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Comparison between pyrrolidinium-based and imidazolium-based dicationic ionic liquids: intermolecular interaction,
Amita Mahapatra1, Manjari Chakraborty1, Sahadev Barik1
1School of Chemical Sciences, National Institute of Science Education and Research, HBNI, P.O. Jatni, Khurda, 752050, Bhubaneswar, Odisha, India. msarkar@niser.ac.in.
This study compares imidazolium and pyrrolidinium dicationic ionic liquids (DILs), revealing distinct structural and dynamic behaviors. Differences in intermolecular interactions and solute-solvent coupling were observed between DILs and their mono-cationic counterparts.
Area of Science:
- Materials Science
- Physical Chemistry
- Spectroscopy
Background:
- Ionic liquids (ILs) are salts with low melting points, widely used as solvents and electrolytes.
- Dicationic ionic liquids (DILs) offer unique properties due to their two cationic centers, influencing intermolecular interactions and structure.
- Understanding the structure-property relationships of DILs is crucial for designing advanced materials.
Purpose of the Study:
- To investigate the differences in intermolecular interactions, microscopic structure, and dynamics between imidazolium-based and pyrrolidinium-based DILs.
- To compare the behavior of DILs with their corresponding mono-cationic ionic liquids (MILs).
- To elucidate the impact of cation structure on DIL properties.
Main Methods:
- Synthesis of two DILs: imidazolium-based and pyrrolidinium-based bis(trifluoromethanesulfonyl)imide.
- Spectroscopic investigations using steady-state and time-resolved fluorescence, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR).
- Comparison of DIL data with corresponding MILs.
Main Results:
- The pyrrolidinium-based DIL exhibits slightly lower polarity than the imidazolium-based DIL.
- Significant differences in solute dynamics were observed between DILs and MILs, indicated by varying rotational correlation times.
- NMR studies revealed a folded alkyl spacer chain in the imidazolium-based DIL and a straight conformation in the pyrrolidinium-based DIL.
Conclusions:
- Microscopic structural organizations differ significantly between imidazolium and pyrrolidinium-based DILs.
- The cation structure profoundly influences the conformational behavior of the alkyl spacer chain in DILs.
- DILs possess distinct characteristics compared to their mono-cationic analogues, driven by their unique structural arrangements.
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