2019
DOI: 10.1021/acs.inorgchem.9b02185
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Low Reorganization Energy for Electron Self-Exchange by a Formally Copper(III,II) Redox Couple

Abstract: The rate constant for electron self-exchange (k 11 ) between LCuOH and [LCuOH] − (L = bis-2,6-(2,6-diisopropylphenyl)carboximidopyridine) was determined using the Marcus cross relation. This work involved measurement of the rate of the cross-reaction between [Bu 4 N][LCuOH] and [Fc][BAr 4F ] (Fc + = ferrocenium; BAr 4 F = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)) by stopped-flow methods at −88 °C in CH 2 Cl 2 and measurement of the equilibrium constant for the redox process by UV−vis titrations under th… Show more

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Cited by 23 publications
(20 citation statements)
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“…Overall, the bond length differences between the precursor and oxidation products are consistent with the loss of an electron from orbitals spanning the Cu center and/or its immediate environment, as reported for less-reactive complexes LCuZ (Z = F, Cl, Br) . Furthermore, the lack of significant structural changes associated with this redox event agrees with the low reorganization energy of 0.95 eV previously measured for the [L H CuOH] − /L H CuOH couple …”
supporting
confidence: 88%
See 1 more Smart Citation
“…Overall, the bond length differences between the precursor and oxidation products are consistent with the loss of an electron from orbitals spanning the Cu center and/or its immediate environment, as reported for less-reactive complexes LCuZ (Z = F, Cl, Br) . Furthermore, the lack of significant structural changes associated with this redox event agrees with the low reorganization energy of 0.95 eV previously measured for the [L H CuOH] − /L H CuOH couple …”
supporting
confidence: 88%
“…Understanding the molecular structures, spectroscopic properties, and reactivity of copper–oxygen complexes is important for gaining insight into the mechanisms by which copper enzymes and other catalysts function. , Among the various complexes studied, those comprising the [CuOH] 2+ core supported by dicarboxamide ligands (Figure ) are notably reactive, attacking C–H and O–H bonds via proton-coupled electron transfer (PCET) processes and undergoing electron transfer at high rates (cf. the rate constant for the reaction of L H CuOH with 1,2-di­hydro­anthracene 50 M –1 s –1 at −25 °C; electron-transfer self-exchange rate constant ∼10 4 M –1 s –1 at −88 °C).…”
mentioning
confidence: 99%
“…S20†). These fast ET rates approach the fastest synthetic mono- and dicopper system (10 5 to 10 6 M −1 s −1 ) 33,35–43 as well as Nature's blue copper ET protein 10 5 to 10 6 M −1 s −1 . 44,45 The corresponding reorganization energies for 4a / 4b and 4b / 4c were calculated to be 1.21(1) eV and 1.21(1) eV using eqn (1) ( Z = 10 11 M −1 s −1 , T = 298 K).…”
Section: Resultsmentioning
confidence: 75%
“…44,45 The corresponding reorganization energies for 4a / 4b and 4b / 4c were calculated to be 1.21(1) eV and 1.21(1) eV using eqn (1) ( Z = 10 11 M −1 s −1 , T = 298 K). 39,46 …”
Section: Resultsmentioning
confidence: 99%
“…CTMs can be integrated in DSCs in the liquid, quasi-solid and solid state. 10 Liquid CTMs or electrolytes in solar cells comprise an organic, aqueous or ionic solvent with a redox couple, for example I À /I 3 À , 345-347 copper 14,95,96,346,[348][349][350][351][352][353] or cobalt 270,284,286,337,[354][355][356] coordination complexes or organic molecules. 357 For DSCs to become commercially viable, significant efforts are being made to develop quasi-solid-and solidstate charge transport materials to ensure sustainability and stability.…”
Section: Charge Transport Materialsmentioning
confidence: 99%