Studies on the effect of solvents on self-assembly of thioctic acid and Mercaptohexanol on gold

In this article we investigated the effect of solvents (CCl₄, CH₃CN, DMF, ethanol, ethanol-H₂O and H₂O) on self-assembly of Thioctic acid (TA) and Mercaptohexanol (MCH) on gold by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Electrochemical characteristics of TA and MCH self-assembled monolayers (SAMs) formed in different solvents were evaluated by inspecting the ions permeability (interfacial capacitance C and phase angle Ф_1 Hz) and electron transfer capability (current density difference Δi and charge transfer resistance R_ct). Experimental results indicated that the ability of solvents availing the ordering of SAMs was: for TA, CCl₄ > ethanol > CH₃CN > ethanol-H₂O > DMF; for MCH, H₂O > ethanol-H₂O ≈ CCl₄ > ethanol ≈ CH₃CN > DMF. Through relating the C, Ф_1 Hz, Δi and R_ct of SAMs (TA and MCH) with parameters of solvent (polarity E_T^N, solubility parameter δ and octanol/water partition coefficients logP_ow), it was found that solvents with bigger logP_ow (smaller E_T^N and δ) availed the ordering of TA-SAMs but the effect of solvents on MCH self-assembly was complex and MCH-SAMs formed in H₂O (the biggest E_T^N, δ and the smallest logP_ow) and CCl₄ (the smallest E_T^N, δ and the biggest logP_ow) were more ordered than in other solvents.