Phosphoryl- and phosphonium-bridged viologens as stable two- and three-electron acceptors for organic electrodes

Bridges, Colin R.; Borys, Andryj M.; Béland, Vanessa A.; Gaffen, Joshua R.; Baumgartner, Thomas

doi:10.1039/d0sc04183a

Cited by 32 publications

(35 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The most-studied systems are the viologen (1,1′-disubstituted-4,4′-bipyridinium salts) and its derivatives, for which many experimental studies have shown intrinsic properties that make them excellent candidates for a series of technological applications [ 35 , 36 , 37 , 38 , 39 , 40 ].…”

Section: Introductionmentioning

confidence: 99%

“…From a theoretical point of view, the studies are scarcer and have concerned some viologen-like [57], dithiolodithiole and thiophene [58], thiophene−pyrrole-containing rings [59], borepins [60], poly-dioxythiophene [61], and methyl ketone [62] systems. It is also worth mentioning certain investigations in which experimental data are coupled to theoretical data, demonstrating how the two approaches can be combined to provide useful insights on these interesting processes [36,39,53,56,[63][64][65][66][67][68][69][70][71].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes

et al. 2021

View full text Add to dashboard Cite

In this review, we provide a brief overview of the contribution that computational studies can offer to the elucidation of the electronic mechanisms responsible for the electrochromism phenomenon, through the use of the density functional theory (DFT) and its time-dependent formulation (TDDFT). Although computational studies on electrochromic systems are not as numerous as those for other physico-chemical processes, we will show their reliability and ability to predict structures, excitation energies, and redox potentials. The results confirm that these methods not only help in the interpretation of experimental data but can also be used for the rational design of molecules with interesting electrochromic properties to be initiated for synthesis and experimental characterization.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes

et al. 2021

View full text Add to dashboard Cite

show abstract

“…More recently, viologens and their derivatives as electron acceptor cations, which can undergo reversible redox reactions, have been explored for electrochemical energy storage. [ 31 , 32 , 33 ] In light of this, the approaches prompt us to construct ionic organic compounds consisting of both redox cations and anions which can undergo reversible multielectron redox reactions to improve their stability and theoretical capacity.…”

Section: Introductionmentioning

confidence: 99%

Biredox‐Ionic Anthraquinone‐Coupled Ethylviologen Composite Enables Reversible Multielectron Redox Chemistry for Li‐Organic Batteries

et al. 2021

View full text Add to dashboard Cite

Organic compounds bearing redox-active ionic pairs as electrode materials for high-performance rechargeable batteries have gained growing attention owing to the properties of synthetic tunability, high theoretical capacity, and low solubility. Herein, an innovative biredox-ionic composite, i.e., ethylviologen dianthraquinone-2-sulfonate (EV-AQ 2 ), affording multiple and reversible active sites as a cathode material in lithium-organic batteries is reported. EV-AQ 2 exhibits a high initial capacity of 199.2 mAh g −1 at 0.1 C rate, which corresponds to the transfer of two electrons from one redox couple EV 2+ /EV 0 and four electrons from two redox-active AQ − anions. It is notable that EV-AQ 2 shows remarkably improved cyclability compared to the precursors. The capacity retention is 89% and the Coulombic efficiency approaches 100% over 120 cycles at 0.5 C rate. The results offer evidence that AQ − into the EV 2+ scaffold with multiple redox sites are promising in developing high-energy-density organic rechargeable batteries.

show abstract

“…They can also be synthesized with a variety of substituents at the nitrogen position that shift their molecular orbital energy levels. Fine-tuning possibilities of colors and redox properties have therefore led to applications in electrochromic devices, molecular machines, , and organic radical batteries. , …”

Section: Introductionmentioning

confidence: 99%

“…Finetuning possibilities of colors and redox properties have therefore led to applications in electrochromic devices, 13 molecular machines, 14,15 and organic radical batteries. 16,17 Solution phase viologens have been extensively characterized by UV−vis 18−20 and resonance Raman spectroscopies 21,22 due to their blue color and by electron paramagnetic resonance (EPR) due to their radical nature. 18,20,23 The dimer has an absorption in the near-infrared and is EPR silent which makes it easily distinguishable from the monomer form.…”

Section: ■ Introductionmentioning

confidence: 99%

Exploring Curious Covalent Bonding: Raman Identification and Thermodynamics of Perpendicular and Parallel Pancake Bonding (Pimers) of Ethyl Viologen Radical Cation Dimers

Juneau

Frenette

2021

J. Phys. Chem. B

View full text Add to dashboard Cite

Viologen radical cations can dimerize in solutions, and the resulting "pimers" were predicted to assemble into parallel and perpendicular conformers by density functional theory (DFT) calculations. Using resonance Raman, we could identify both perpendicular and parallel forms of ethyl viologen dimers. The distinction between the two forms was accomplished by studying the formation of a host−guest complex with γ-cyclodextrin. The dimer's perpendicular form was excluded due to the host cavity size, and γ-cyclodextrin addition caused a decrease in peak intensities at 1171, 1511, and 1602 cm −1 that could be assigned to the perpendicular form. DFT modeling of the vibrational spectra under preresonance conditions allowed us to assign the remaining vibrational modes for the parallel and perpendicular forms. Using variable-temperature UV−vis, the bond dissociation energy (ΔH) for this pancake-bonded dimer was measured as 13.1 ± 0.2 kcal/ mol. This type of covalent pancake bonding is a challenge to properly describe using DFT methods. Previously, B97D was found to best describe the ΔG of this dimerization (Angew. Chem. 2017, 129, 9563−9567), but this method underestimates the ΔH by 6 kcal/mol. Of the 11 functionals tested, we found that B3LYP with Grimme's D3 dispersion effect can best reproduce the ΔH. Energy decomposition analysis of the bonding energy showed that solvation effects were the most important contributorpolar solvents are needed to overcome the Coulomb repulsion between the two positively charged monomers. Dispersion effects are second in importance and appear larger than the favorable orbital interaction obtained by singly occupied molecular orbital (SOMO)−SOMO orbital overlap. This study brings forth important insights into the curious cases of covalent bonding between two π-delocalized radicals.

show abstract

Phosphoryl- and phosphonium-bridged viologens as stable two- and three-electron acceptors for organic electrodes

Abstract: Two strongly electron-accepting viologens, including an intriguing tricationic species, are reported. The utility of the tricationic viologen for energy storage has been showcased via use as electrode in a proof-of-concept battery.

Cited by 32 publications

References 21 publications

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes

Biredox‐Ionic Anthraquinone‐Coupled Ethylviologen Composite Enables Reversible Multielectron Redox Chemistry for Li‐Organic Batteries

Exploring Curious Covalent Bonding: Raman Identification and Thermodynamics of Perpendicular and Parallel Pancake Bonding (Pimers) of Ethyl Viologen Radical Cation Dimers

Contact Info

Product

Resources

About