Variables of the Analytical Electrochemical Data Acquisition for Boron Subphthalocyanines

Abstract

The electrochemical behavior of boron subphthalocyanines (BsubPcs) has been investigated using cyclic voltammetry in the presence of various solvents, internal standards, supporting electrolytes, working electrodes, and sweep voltage scan rates. We have focused on halogenated BsubPcs (Cl−Cl6BsubPc, Cl−Cl12BsubPc, F−F6BsubPc, F−F12BsubPc) and a non‐halogenated baseline (Cl−BsubPc). Halogenated BsubPcs are of interest to the field due to their promising advances as organic electronic materials for applications based on redox or electron transfer processes. We had pre‐established a standard operating procedure (SOP) for electrochemical data acquisition, but it was timely to consider alternative variables, their impact on the electrochemical data and re‐establish an alternative SOP. We observed modest shifts (up to 49 mV) of the BsubPc redox potentials when changing the internal standard, working electrode and/or the electrolyte concentration. In scan rate range between 20 and 250 mV s−1, the peak (ir)reversibility for F−F6BsubPc and F−F12BsubPc remained unchanged and the electron transfers at the surface electrode remained diffusion‐controlled.

Cs-Symmetric, Peripherally Fluorinated Boron Subphthalocyanine–Subnaphthalocyanine Hybrids: Shedding New Light on Their Fundamental Photophysical Properties and Their Functionality as Optoelectronic Materials

“…The electrochemical properties of fully fluorinated F-F 12 BsubPc were used as a comparison point in analyzing the electrochemical properties of the peripherally fluorinated hybrids. For CV, we found that F-F 12 BsubPc had an irreversible oxidation potential at 1.536 V and two reversible reduction potentials at −0.460 V ( E 1/2,red 1 ) and −1.158 V ( E 1/2,red 2 ); these results are in excellent agreement with previously collected electrochemical data for F-F 12 BsubPc in similar CV conditions . Similar to F-F 12 BsubPc, both axially fluorinated hybrids, F-F 8 Bsub­(Pc 2 -Nc 1 ) and F-F 8 BsubPc, exhibit two reversible reduction potentials.…”

“…The CV traces presented in this manuscript represent the trace of the third cycle. The resulting CV potentials were corrected to the half-wave oxidation potential of ferrocene/ferrocenium (Fc/Fc + ) ( E 1/2,ox = 0.547 V vs Ag/AgCl , ) that was used as an internal reference. For DPV, all potentials were corrected to the maximum potential of ferrocene, which was calculated to be 0.522 V vs Ag/AgCl using the following equation: E max = E 1 / 2 − normalΔ E 2 , where E max is the maximum potential, E 1/2 is the known half-wave potential, and Δ E is the pulse amplitude .…”

Recent advances in subphthalocyanines and related subporphyrinoids

“…The impact of different experimental variables such as the nature of solvents, internal standards and electrolytes, the type of working electrodes and the scan rate on the electrochemical behavior of various SubPc derivatives was systematically investigated by Bender and co-workers, who established a standard operating procedure for data acquisition. 208…”

“…80,83,206,207 The impact of different experimental variables such as the nature of solvents, internal standards and electrolytes, the type of working electrodes and the scan rate on the electrochemical behavior of various SubPc derivatives was systematically investigated by Bender and co-workers, who established a standard operating procedure for data acquisition. 208 The redox gap of SubPc is larger than that of Pcs, being the former of about 2.1 eV and the latter of approximately 1.7 eV. 1 Several techniques have been employed for the estimation of the absolute HOMO and LUMO energy levels of SubPcs, such as cyclic voltammetry in solution or photoelectron spectroscopy onto highly ordered pyrolytic graphite (HOPG) substrates.…”

Modulating the Electron Transporting Properties of Subphthalocyanines for Inverted Perovskite Solar Cells

“…For this purpose, we prepared and evaluated three different SubPcs ( Figure 1 ) with varying electronic and supramolecular properties. In particular, we synthetize SubPcs functionalized with either six or twelve peripheral fluorine or chlorine atoms ( Cl-SubPcF 6 , Cl-SubPcF 12, and Cl-SubPcCl 12 ), since it has been previously demonstrated that they present good supramolecular organization and low-lying LUMO levels ( Bukuroshi et al, 2021 ). In combination with C 60 , these SubPc materials are then implemented as ETM in PSC devices based on a solution processed PVK (CsFAMAPbIBr) active layer.…”