Proof of ion-pair structures in ammonium-based protic ionic liquids using combined NMR and DFT/PCM-based chemical shift calculations

Literature Information

Publication Date 2017-08-09
DOI 10.1039/C7CP04481J
Impact Factor 3.676
Authors

M. Lozynski, J. Pernak, Z. Gdaniec, B. Gorska, F. Béguin


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Abstract

The self-assembly of triethylammonium bis(trifluoromethylsulfonyl)imide, i.e. [(C2H5)3NH][TFSI], in chloroform and aqueous solutions has been investigated using 1H NMR spectroscopy and computational (DFT/PCM prediction) methods. We have examined a number of ion pairs formed between the [(C2H5)3NH]+ cation with different conformations of alkyl substituents as well as various dispositions of the multi-site [TFSI]− anion. Based on the agreement between the calculated (DFT) and observed 1H NMR chemical shifts, [(C2H5)3NH][TFSI] in chloroform formed lipophilic complexes with effective N+–H⋯N or N+–H⋯O hydrogen bonding, whereas hydrophilic complexes with Cα–H⋯O and Cα–H⋯F hydrogen bonding are found in aqueous solutions. This study provides a new insight into the self-aggregation of ammonium PILs incorporating the widely used [TFSI]− anion and demonstrates the importance of solvent effects on chemical shifts. The simulations with explicit and implicit dielectric continuum solvents are found to be the most realistic method, yielding a representative ensemble of structures.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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