The Fundamental and Underrated Role of the Base Electrolyte in the Polymerization Mechanism. The Resorcinol Case Study

Abstract

The Kane–Maguire polymerization mechanism is disassembled at a molecular level by using DFT-based quantum mechanical calculations. Resorcinol electropolymerization is selected as a case study. Stationary points (transition states and intermediate species) leading to the formation of the dimer are found on the potential energy surface (PES), and elementary reactions involved in the dimer formation are characterized. The latter allow to further propagate the polymerization chain reaction, when applied recursively. In this paper, the fundamental role of the sulfate anion (a typical base electrolyte) is addressed. Investigation of the PES in terms of both stationary-state properties and of ab initio molecular dynamics results (dynamic reaction coordinate) allows the appreciation in detail of the critical role of the base electrolyte anion in making the proton dissociation from the initial radical ion, a feasible (downhill in energy) process.

Chiral “doped” MOFs: an electrochemical and theoretical integrated study

“…In particular, the electrochemical behaviour was studied by performing cyclic voltammetry (CV) measurements using a solid-state electrochemical approach ( Solano et al, 2021 ; Solano et al, 2022 ). Typically, electrochemical-based CV measurements are exploited to study the electrochemical behaviour of metals and organic compounds in bulk solution ( Bonechi et al, 2021b ; Stefani et al, 2021 ; Giurlani et al, 2022b ; Bonechi et al, 2022 ), or using commercial systems of the electroplating industry ( Berretti et al, 2020 ; Mariani et al, 2022 ; Comparini et al, 2023 ). In this study we adopted a new custom-designed setup to probe the crystal electrochemical behaviour, to avoid the dissolution of the solid-state material.…”

Molecular electrochemistry. An overview of a cross-field: Electrochemistry/spectroscopic/theoretical integrated approach

“…Thus, the synergy of conventional electrochemical experiments, the complementary synergetic approach opens the door to exploration and understanding the hidden aspects of the electrochemical processes beyond a traditional experimental frame. [16,[20][21][22][23] The most significant demonstrations are summarized herein.…”

On the Dynamics of the Carbon–Bromine Bond Dissociation in the 1-Bromo-2-Methylnaphthalene Radical Anion

“…On the other hand, the concerted mechanism involves direct production of a bromide anion and an organic radical without the formation of any intermediate state. The existence of a stepwise or concerted reaction path depends on different parameters, such as the nature of the investigated halide, the solvent and the influence of the supporting electrolyte [ 24 ]. In the scenario of aromatic halides, the stepwise reaction is, in general, the preferred dissociation pathway [ 25 ].…”

“…The existence of a stepwise or concerted reaction path depends on different parameters, such as the nature of the investigated halide, the solvent and the influence of the supporting electrolyte [24]. In the scenario of aromatic halides, the stepwise reaction is, in general, the preferred dissociation pathway [25].…”