Computational insights into the molecular interaction and ion-pair structures of a novel zinc-functionalized ionic liquid, [Emim][Zn(TFSI)3]

•Elucidation of the most probable structure of a novel zinc-functionalized ionic liquid•Fundamental understanding of the molecular interaction in [Emim][Zn(TFSI)3]•Systematic analysis of the simulated and experimental IR spectra•Complete assignment of vibrational modes guided by DFT calculations

The ion pair structures of a novel CO2 capture material in the form of a metal chelate anion-containing room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tri[bis(trifluoromethylsulfonyl)imide]zincate(II), [Emim][Zn(TFSI)3], were elucidated by correlating the infrared spectra generated using density functional theory (DFT) calculations with the experimental spectrum derived from a room temperature infrared spectroscopic measurement. A free volume energy minimization algorithm revealed stable structures where the zinc ion forms an octahedral, homoleptic complex with the ligand bis(trifluoromethylsulfonyl)imide through coordination with the oxygen of the sulfone group, with 1-ethyl-3-methylimidazolium acting as the counterion. The method of analysis was built around 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [Emim][TFSI], involving direct comparison with published data, and extended to the more complex [Emim][Zn(TFSI)3] system. The DFT calculations reproduced the vibrational spectra of [Emim][Zn(TFSI)3] and [Emim][TFSI] using their optimized geometries, with correlation slopes of 0.9996 and 1.0022, respectively. Comparison of the vibrational modes of [Emim][TFSI] and [Emim][Zn(TFSI)3] provided insights into the ion pair structure of, and molecular interactions in the ILs analyzed.

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