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The Role of Amide-π Stacking in Resolving the DMF-Benzene Miscibility Paradox.
Zhi-Ying Zhao1,2, Ting Chen1,2, Kang Zhou3
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China.
The Journal of Physical Chemistry Letters
|October 15, 2025
Summary
Polar N,N-dimethylformamide (DMF) and nonpolar benzene (PhH) miscibility is explained by amide-π interactions. These interactions, identified through computational and database analysis, are key to understanding solvent behavior in chemistry.
Area of Science:
- Physical Chemistry
- Computational Chemistry
- Supramolecular Chemistry
Background:
- The "like-dissolves-like" principle traditionally explains solvent miscibility.
- The miscibility of polar N,N-dimethylformamide (DMF) with nonpolar benzene (PhH) contradicts this principle, necessitating a molecular-level explanation.
Purpose of the Study:
- To elucidate the molecular interactions driving the miscibility of DMF and PhH.
- To identify and characterize the role of amide-π interactions in this solvent system.
Main Methods:
- First-principles calculations to model DMF-PhH interactions and alignments.
- Energy decomposition analysis to quantify interaction forces.
- Statistical analysis of the Cambridge Structural Database to assess interaction generality.
Main Results:
- Identified near-parallel DMF-PhH alignment driven by amide-π interactions.
- Quantified amide-π interaction energy as intermediate between π-π stacking and hydrogen bonding.
- Demonstrated the structural prevalence and universality of amide-π interactions.
Conclusions:
- Amide-π interactions are the primary drivers of DMF-PhH miscibility, resolving a paradox.
- Amide-π interactions represent a universal solvation mechanism with implications for synthetic chemistry.
- Provides theoretical guidance for rational solvent selection in chemical synthesis.
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