Impact of imidazolium-based ionic liquid, functionalized with aromatic compounds, on thermophysical and aggregation properties

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-04-11 DOI:10.1016/j.molliq.2025.127579

Victor S. Pereira , Thaíssa S. Beck , Letícia Zibetti , Bruno S.C. Santos , Amanda C. Moraes , Caroline R. Bender , Marcos A. Villetti , Helio G. Bonacorso , Clarissa P. Frizzo

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Abstract

New imidazolium-based ionic liquids ([But(MIM)Br][Br]) functionalized with aromatic compounds (clioquinol, 1-naphthol, 2,4-dibromophenol, and eugenol) were synthesized at excellent yields (81–94 %). Thermal stability was evaluated, and it was found that the ionic liquids (ILs) were stabler than their aromatic precursors — the least stable decomposed at 152 °C and the most stable at 241 °C. The ILs had greater water solubility than their aromatic precursors and a higher density than water. The self-assembly properties of the ILs in an aqueous medium were determined, and the free energy of aggregation values indicated that the aggregation process was exergonic. The order of the critical aggregation concentrations, which are related to the hydrophobicity of the ILs, were as follows: [DBPB(MIM)][Br] < [CliB(MIM)][Br] = [NaphtB(MIM)][Br] < [EgB(MIM)][Br]. The contact angle of the samples with the PET surface, spreading coefficient, and surface free energy were used to evaluate the ILs’ hydrophobicity. In this IL series, [DBPB(MIM)][Br] had the highest hydrophobicity and the greatest tendency to form aggregates in water (lower critical aggregation concentration). By contrast, [EgB(MIM)][Br] had the lowest hydrophobicity and the least tendency to self-organize in solution. Our results highlight the influence that different aromatic compounds have on the physicochemical properties of ILs in polar solvents.

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芳香族化合物功能化的咪唑基离子液体对其热物理和聚集性能的影响

以芳香化合物（氯喹啉、1-萘酚、2,4-二溴酚和丁香酚）为功能化剂，合成了新型咪唑基离子液体[But(MIM)Br][Br]，收率高达81 ~ 94%。对离子液体的热稳定性进行了评价，发现离子液体比芳香前驱体更稳定，在152℃分解时最不稳定，在241℃分解时最稳定。其水溶性比芳香前体大，密度比水大。测定了聚合物在水介质中的自组装性能，并测定了聚合值的自由能，结果表明聚合物在水介质中的自组装过程是自能式的。临界聚集浓度的强弱顺序依次为：[DBPB(MIM)][Br] <；[CliB(MIM)][Br] = [NaphtB(MIM)][Br] <；(银杏叶提取物(MIM)] (Br)。用样品与PET表面的接触角、扩散系数和表面自由能来评价其疏水性。在该IL系列中，[DBPB(MIM)][Br]的疏水性最高，在水中形成聚集的倾向最大（临界聚集浓度较低）。而[EgB(MIM)][Br]的疏水性最低，在溶液中自组织倾向最小。我们的结果强调了不同芳香族化合物对极性溶剂中il的物理化学性质的影响。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.