Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Peljo, Pekka; Qiao, Liang; Murtomäki, Lasse; Johans, Christoffer; Kontturi, Kyösti

doi:10.1002/cphc.201200953

Cited by 20 publications

(16 citation statements)

References 29 publications

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“…For example, the replacement of TB − with tetraphenylborate (TPB − ) results in the positive end of the PPW being limited by transfer of TPB − from organic to aqueous phase. A sufficiently polar organic solvent, typically 1,2-dichloroethane (DCE), 41 1,2-dichlorobenzene (DCB), 42,43 or α,α,α-trifluorotoluene (TFT) 44 having relative permittivities (ε) of 10.4, 10.1, or 9.2, 45 respectively, is often required to facilitate dissociation of the organic electrolyte salt as well as to support the flow of current. However, even chloroform 46,47 or toluene, 48 which have low values of ε (4.8 and 2.4, respectively), can be used at microinterfaces, where the low conductivity of the organic solvent is not a significant issue.…”

Section: Interface Between Two Immisciblementioning

confidence: 99%

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

et al. 2018

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The functionality of liquid-liquid interfaces formed between two immiscible electrolyte solutions (ITIES) can be markedly enhanced by modification with supramolecular assemblies or solid nanomaterials. The focus of this Review is recent progress involving ITIES modified with floating assemblies of gold nanoparticles or "nanofilms". Experimental methods to controllably modify liquid-liquid interfaces with gold nanofilms are detailed. Also, we outline an array of techniques to characterize these gold nanofilms in terms of their physiochemical properties (such as reflectivity, conductivity, catalytic activity, or plasmonic properties) and physical interfacial properties (for example, interparticle spacing and immersion depth at the interface). The ability of floating gold nanofilms to impact a diverse range of fields is demonstrated: in particular, redox electrocatalysis, surface-enhanced Raman spectroscopy (SERS) or surface plasmon resonance (SPR) based sensors, and electrovariable optical devices. Finally, perspectives on applications beyond the state-of-the-art are provided.

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Section: Interface Between Two Immisciblementioning

confidence: 99%

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

et al. 2018

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“…As for peaks P2a and P2b, little change was observed with time. Noting the partition coefficient of FcCH 2 OH ( P =82) in the system of 1,2‐dichlorobenzene and aqueous HCl 21 , FcCH 2 OH is likely to be much more soluble in the organic phase than in the aqueous phase. For other pretreatment times of 1 to 10 min, peaks P1 and P2 behaved in a similar manner.…”

Section: Resultsmentioning

confidence: 99%

The Measurement of the Gibbs Energy of Transfer Between Oil and Water Using a Nano‐Carbon Paste Electrode

et al. 2013

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The use of nano‐carbon paste electrodes for the measurement of Gibbs energies of transfer between oil and aqueous phases is reported. In this method the oil of interest is used as the binder for the nano‐carbon paste electrodes and the molecule of interest is dissolved in the organic or aqueous phase. Voltammetry is performed over a period of time and used to monitor the transfer of the molecule between the two phases. The method is illustrated for the transfer of ferrocenemethanol between water and oil using the ferrocenemethanol / ferroceniummethanol (FcCH2OH/FcCH2OH+) redox couple. Three pairs of voltammetric peaks were observed in a 0.1 M KCl solution when the nano‐carbon paste electrode was modified by dissolution of FcCH2OH in the binder oil: P1 [E=0.23 V, 0.17 V vs. Ag/AgCl (1 M KCl)], P2 [E=0.36 V, 0.32 V vs. Ag/AgCl (1 M KCl)] and P3 [E=0.55 V, 0.46 V vs. Ag/AgCl (1 M KCl)]. These are assigned to the FcCH2OH species existing in the aqueous solution [FcCH2OH(aq)/FcCH2OH+(aq)], originating in the oil (o) [FcCH2OH(o)/FcCH2OH+(aq)] and to oxidation of adsorbed (ads) material on the nano‐carbon [FcCH2OH(ads)] respectively. When supporting electrolyte containing the anions Cl−, NO3− or SCN− was used, an expulsion of the oxidised ferrocene occurred and the difference in midpoint potentials (Emid) between the peaks P1 and P2 observed in these experiments allowed the calculation of the Gibbs energy (ΔG°) of transfer of ferrocenemethanol from water to oil. The average ΔG° value thus obtained was (−12.7±0.2) kJ mol−1. For more hydrophobic anions (X−=PF6−, AsF6−), the electron transfer is coupled to the transfer of the anion into the oil and the ΔG° for the transfer of the ion pair of FcCH2OH+ and X− ions from water to oil was found to be −1.3 and −3.9 kJ mol−1 for PF6− and AsF6− respectively.

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“…Various reviews and publications [1][2][3][4] give a detailed ac-count on its importance and applicability. These processes help us in explaining various photophysical, photobiological and photochemical changes occurring in different environments [5,6]. Among this keto-enol tautomerisation involving proton transfers within the DNA are considered the pathway of spontaneous mutations [7].…”

Section: Introductionmentioning

confidence: 99%

Tautomers of homophthalic anhydride in the ground and excited electronic states: analysis through energy, hardness and vibrational signatures

Dey

Chakraborty

2020

J Mol Model

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The keto-enol tautomerisation in homophthalic anhydride (HA) is investigated in the ground (S 0 ) and excited (S 1 ) electronic states. The keto form with a dicarbonyl structure is found to be the most stable form in S 0 and enol form with a monocarbonyl structure in S 1 indicating an excited state intramolecular proton transfer (ESIPT) process. The computed results show consistency with the change in basis sets and methods of calculations. Apart from the two tautomers, transition states are also identified. The barrier to interconversion is found to reduce substantially in S 1 . Internal reaction coordinate (IRC) calculations confirm the pathway of interconversion between the two forms in S 0 and S 1 . The observed FT-IR spectra corroborate well with our computed spectra. The appearance of two strong lines around 1800 cm −1 confirms the lowest energy structure to be the keto tautomer with a dicarbonyl form in S 0 . Our computations corroborate well with the crystal structure data for an analogous molecule. Electron distribution in HOMO and LUMO indicate the excitation process as π → π * in nature. The qualitative chemical concepts like hardness and electrophilicity are calculated to estimate the stability of the tautomers. The energy and hardness profiles with the variation of IRC are opposite to each other, verifying the principle of maximum hardness.

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Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Cited by 20 publications

References 29 publications

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

The Measurement of the Gibbs Energy of Transfer Between Oil and Water Using a Nano‐Carbon Paste Electrode

Tautomers of homophthalic anhydride in the ground and excited electronic states: analysis through energy, hardness and vibrational signatures

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