Study of Molecules with Multiple Redox Centers Using Differential Staircase Voltammetry at Spherical Electrodes and Microelectrodes

López‐Tenés, Manuela; Serna, Carmen; Moreno, Marién M.; Molina, Á.

doi:10.4152/pea.200701103

Cited by 9 publications

(7 citation statements)

References 18 publications

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“…From Eq. (24), the response in staircase cyclic voltammetry (SCV) [16] can be calculated, taking into account that the potential perturbation for this technique is given by:…”

Section: Staircase Cyclic Voltammetry and Cyclic Voltammetrymentioning

confidence: 99%

“…The features of the cyclic voltammograms of the 9-member square mechanism are investigated at electrodes of different geometry under transient and steady state conditions for different values of the formal potentials and for distinctly different chemical stabilisation of the three redox states. Depending on the electrode geometry and the difference between the formal potentials, appropriate procedures based on cyclic voltammetry [14,15] and differential cyclic voltammetry [16] are established to elucidate the chemistry of the redox species in solution and to determine the corresponding equilibrium constants.…”

Section: Introductionmentioning

confidence: 99%

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Staircase, cyclic and differential voltammetries of the nine-member square scheme at microelectrodes of any geometry with arbitrary chemical stabilization of the three redox states

Molina

Laborda

Gómez-Gil

et al. 2016

J Solid State Electrochem

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Simple analytical expressions are deduced for the cyclic (staircase) and differential cyclic (staircase) voltammetric responses of the 9-member square scheme at the most widely-used microelectrode geometries: disc, (hemi)spheres, cylinders and bands. The generality of the reaction scheme considered enables us to tackle many different and common electrochemical situations where the oxidized, intermediate and/or reduced species of a two-electron transfer also take part in homogeneous chemical equilibria such as protonations, complexations or ion pairings. The effect of the coupled chemical processes on the voltammograms is analyzed at electrodes of different size and shape under a variety of conditions depending on which redox state is chemically stabilized most significantly. Also, working curves for the determination of the formal potentials and the chemical equilibrium constants are given for macro-, micro-and ultramicro-electrodes in cyclic voltammetry and differential cyclic voltammetry.

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“…From Eq. (24), the response in staircase cyclic voltammetry (SCV) [16] can be calculated, taking into account that the potential perturbation for this technique is given by:…”

Section: Staircase Cyclic Voltammetry and Cyclic Voltammetrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Staircase, cyclic and differential voltammetries of the nine-member square scheme at microelectrodes of any geometry with arbitrary chemical stabilization of the three redox states

Molina

Laborda

Gómez-Gil

et al. 2016

J Solid State Electrochem

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“…It is of course first of all a function of the nature of the linker between them, i. e . double bond(s), triple bond(s), (hetero)aromatic ring(s), aliphatic chain… or none (redox centres directly linked), as highlighted in many studies (like e. g [15–29] …”

Section: Introductionmentioning

confidence: 99%

“…Communication between equivalent redox centres in electroactive molecules is a fundamental and fascinating subject. [15][16][17][18] It is of course first of all a function of the nature of the linker between them, i. e. double bond(s), triple bond(s), (hetero)aromatic ring(s), aliphatic chain… or none (redox centres directly linked), as highlighted in many studies (like e. g. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] ).…”

Section: Introductionmentioning

confidence: 99%

Trópos and Átropos Biindole Chiral Electroactive Monomers: A Voltammetry and HPLC Comparative Insight

et al. 2022

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A series of 2,2’‐biindole‐based inherently chiral electroactive monomers are comparatively investigated with their 3,3’ analogues as an excellent study case of two equivalent redox centres interacting through a torsional barrier. The twin peak potential splitting observed in voltammetry for the first oxidation of the biheteroaromatic core accounts for the energy barrier height: the lower the barrier, the larger the peak potential splitting, with modulation by solvent and temperature. The height of the energy barrier is determining for the electrochemical and spectroscopic features of the monomers as well as for their configurational stability and applicability for enantioselection purposes. The 3,3’ monomers, featuring large twin peak splittings in CV, are “trópos” systems with a low torsional barrier, so they cannot exist as stable enantiomers at room temperature. Instead their 2,2’ isomers, with much smaller twin peak splittings, are “átropos” systems and can be separated by enantioselective HPLC into stable enantiomers, providing powerful “inherently chiral” selectors with outstanding enantioselection properties in chiral electroanalysis and electrochemistry as well as in chiroptical spectroscopy, with fascinating reciprocal correlations.

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“…The presence of stepwise electron transfer mechanisms is proclaimed in numerous applied systems like dyes, dendrimers, polymers, enzymes, − and so forth. Many of these systems frequently encounter the double step charge transfer processes, popularly known as EE mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Theory for Cyclic Staircase Voltammetry of Two Step Charge Transfer Mechanism at Rough Electrodes

Parveen

Kant

2016

J. Phys. Chem. C

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We have developed theory for cyclic (staircase) voltammetry (CSCV) of a two step reversible charge transfer (EE) mechanism for redox species with unequal diffusion coefficients at rough electrodes. The various surface microscopies provide details of random morphology of the electrode which is characterized through the power spectrum in our theory. For the finite fractal electrode model, anomalous enhancement and scan rate dependence of the CSCV or CV response is caused by fractal dimension (D H ), lower length scale of fractality ( ), and topothesy length ( τ). The peak current corresponding to both charge transfer steps is enhanced with an increase in roughness of the fractal electrode (through increase in D H or τ or decrease in ). The onset and offset of the anomalous regime is controlled by τ and , respectively. Results show that the electrode roughness has the potential to enhance the sensitivity of CSCV as an analytical technique. This is due to a decrease in the difference between the peak currents of two charge transfer steps and an increase in the ratio of the peak to the valley (minimum existing between the two peaks) current in the presence of roughness. Finally, we show that not accounting for roughness in data analysis may cause errors in estimation of composition, diffusion coefficient, improper assignment of electrode mechanism, and so forth.

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Study of Molecules with Multiple Redox Centers Using Differential Staircase Voltammetry at Spherical Electrodes and Microelectrodes

Cited by 9 publications

References 18 publications

Staircase, cyclic and differential voltammetries of the nine-member square scheme at microelectrodes of any geometry with arbitrary chemical stabilization of the three redox states

Staircase, cyclic and differential voltammetries of the nine-member square scheme at microelectrodes of any geometry with arbitrary chemical stabilization of the three redox states

Trópos and Átropos Biindole Chiral Electroactive Monomers: A Voltammetry and HPLC Comparative Insight

Theory for Cyclic Staircase Voltammetry of Two Step Charge Transfer Mechanism at Rough Electrodes

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