Vaz Inês C M, Bastos Margarida, Bernardes Carlos E S, Canongia Lopes José N, Santos Luís M N B F
Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, P-4169-007 Porto, Portugal.
Phys Chem Chem Phys. 2018 Jan 24;20(4):2536-2548. doi: 10.1039/c7cp07525a.
In this work, we studied the effect of anion and cation properties on the interaction of alcohols with ionic liquids (ILs), using propan-1-ol as a molecular probe. The enthalpies of solution at infinite dilution of propan-1-ol in several ILs were measured by isothermal titration calorimetry (ITC). The calorimetric results were analysed together with molecular dynamics simulation and quantum chemical calculations of the interaction of the hydroxyl group of propan-1-ol with the anions. The results evidenced the role of the anion's basicity in the intermolecular interactions of alcohols and ionic liquids and further revealed a secondary effect of the cation nature on the solvation process. The effect of the anion basicity on the strength of the interaction of alcohols with ionic liquids was evaluated by comparing the results obtained for ILs with the same cation and different anions, [CCim][anion] (anions NTf, PF, FAP, DCA and TFA). The effect of the cation (size, aromaticity, charge distribution, and acidity) was explored using five different cations of the NTf series, [cation][NTf] (cations CCim, CCpirr, Cpy, CCpip, and CCCim).
在本研究中，我们以丙醇为分子探针，研究了阴离子和阳离子性质对醇类与离子液体（ILs）相互作用的影响。通过等温滴定量热法（ITC）测量了丙醇在几种离子液体中的无限稀释溶解焓。结合分子动力学模拟以及丙醇羟基与阴离子相互作用的量子化学计算对量热结果进行了分析。结果证明了阴离子碱性在醇类与离子液体分子间相互作用中的作用，并进一步揭示了阳离子性质对溶剂化过程的次要影响。通过比较具有相同阳离子和不同阴离子（[CCim][阴离子]，阴离子为NTf、PF、FAP、DCA和TFA）的离子液体所获得的结果，评估了阴离子碱性对醇类与离子液体相互作用强度的影响。使用NTf系列的五种不同阳离子（[阳离子][NTf]，阳离子为CCim、CCpirr、Cpy、CCpip和CCCim）探究了阳离子（大小、芳香性、电荷分布和酸度）的影响。
