Computational Approach to Understanding the Electrocatalytic Reaction Mechanism for the Process of Electrochemical Oxidation of Nitrite at a Ni–Co-Based Heterometallo-Supramolecular Polymer

[Image: see text] Here, we report a semiempirical quantum chemistry computational approach to understanding the electrocatalytic reaction mechanism (ERM) of a metallic supramolecular polymer (SMP) with nitrite through UV/vis spectral simulations of SMP with different metal oxidation states before and after interactions with nitrite. In one of our recent works, by analyzing the electrochemical experimental data, we showed that computational cyclic voltammetry simulation (CCVS) can be used to predict the possible ERM of heterometallo-SMP (HMSMP) during electrochemical oxidation of nitrite ( T. IslamACS Appl. Polym. Mater.2020, 2( (2), ), 273−284). However, CCVS cannot predict how the ERM happens at the molecular level. Thus, in this work, we simulated the interactions between the repeating unit (RU) of the HMSMP polyNiCo and nitrite to understand how the oxidation process took place at the molecular level. The RU for studying the ERM was confirmed through comparing the simulated UV/vis and IR spectra with the experimental spectra. Then, the simulations between the RU of the polyNiCo and various species of nitrite were done for gaining insights into the ERM. The simulations revealed that the first electron transfer (ET) occurred through coordination of NO(2)(–) with either of the metal centers during the two-electron-transfer oxidation of nitrite, while the second ET followed a ligand–ligand charge transfer (LLCT) and metal–ligand charge transfer (MLCT) pathway between the NO(2) species and the RU. This ET pathway has been proposed by analyzing the transition states (TSs), simulated UV/vis spectra, energy of the optimized systems, and highest occupied molecular orbital–lowest occupied molecular orbital (HOMO–LUMO) interactions from the simulations between the RU and nitrite species.