Molecular engineering of the electronic, structural, and electrochemical properties of nanostructured 1-methyl-4-phenyl 1,2,4 triazolium-based [PhMTZ][X1–10] ionic liquids through anionic changing

Abstract

In the present work, molecular engineering of the physicochemical characteristics of ion pairing in 1-methyl-4-phenyl 1,2,4 triazolium-based ionic liquids [PhMTZ][X] (X1–10 = CH3CO2 −, Cl−, NO3 −, CF3CO2 −, BF4 −, ClO4 −, N(CN)2 −, PF6 −, NTf2 −, and C(CN)3 −) are explored using at M06-2X/6–311++G(d,p) level. The binding Gibbs free energy of ion pairs are reevaluated using ab initio MP2 method and dispersion corrected M06-2X-D3, B2PLYP, B2PLYP-D, and mPW2PLYP-D functionals. Comparison of Gibbs free bottom electrodes (BEs) calculated by B2PLYP and B2PLYP-D functionals reveals that the contribution of dispersion energy to the total BEs vary from 9% for X1 to 17% for X = 10. Besides, the range of the dispersion contribution estimated by M06-2X-D3 functional is found to be 0.6% for X2 to 5% for X3. The Gibbs free BEs in solvent media, Gibbs free energy and enthalpy of formation, electrochemical windows, anodic and cathodic stability, volumetric and electron density properties, charge transfer values, and electrostatic maps are evaluated.