Modulating electron transfer in ferrocene-naphthoquinone dyads: New insights in parameters influencing ET efficiency

Sabuzi, Federica; Coletti, Alessia; Pomarico, Giuseppe; Floris, Barbara; Galloni, Pierluca; Conte, Valeria

doi:10.1016/j.jorganchem.2019.02.001

Cited by 7 publications

(5 citation statements)

References 39 publications

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“… 26 , 27 Among these, Sc 3+ ions demonstrated the strongest effect, decreasing the energetic level of the first reduction, thus enabling electron transfer processes that would not take place in their absence. 26 − 28 Accordingly, the effect of Sc 3+ on the KuQuinone redox behavior has been investigated. In the case of KuQuinones, DFT calculations performed using the B3LYP functional and LANL2DZ basis set revealed that in CH 2 Cl 2 , the exclusive coordination site for scandium ions is carbonyl oxygen (C).…”

Section: Resultsmentioning

confidence: 99%

“…As discussed above, quinone reduction potentials are strongly affected by several factors that can facilitate their reduction processes. Besides hydrogen bond donor additives, Lewis acids, such as Mg 2+ , Y 3+ , and Sc 3+ ions, can also coordinate quinone carbonyl oxygens. , Among these, Sc 3+ ions demonstrated the strongest effect, decreasing the energetic level of the first reduction, thus enabling electron transfer processes that would not take place in their absence. − Accordingly, the effect of Sc 3+ on the KuQuinone redox behavior has been investigated. In the case of KuQuinones, DFT calculations performed using the B3LYP functional and LANL2DZ basis set revealed that in CH 2 Cl 2 , the exclusive coordination site for scandium ions is carbonyl oxygen (C).…”

Section: Resultsmentioning

confidence: 99%

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Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study

et al. 2021

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The study of the electrochemical properties of variegated quinones is a fascinating topic in chemistry. In fact, redox reactions occurring with quinoid scaffolds are essential for most of their applications in biological systems, in photoelectrochemical devices, and in many other fields. In this paper, a detailed investigation of KuQuinones’ redox behavior is presented. The distinctiveness of such molecules is the presence in the structure of two condensed naphthoquinone units, which implies the possibility to undergo multiple one-electron reduction processes. Solvent, supporting electrolyte, and hydrogen bond donor species effects have been elucidated. Changing the experimental parameters provoked significant shift of the redox potential for each reduction process. In particular, additions of 2,2,2-trifluoroethanol as a hydrogen bond donor in solution as well as Lewis acid coordination were crucial to obtain important shifts of the redox potentials toward more favorable values. UV–vis–NIR spectroelectrochemical experiments and DFT calculations are also presented to clarify the nature of the reduced species in solution.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study

et al. 2021

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“…Furthermore, PET is aborted upon oxidation of ferrocene to its ferricenium form, resulting in fluorescence emission enhancement. In this respect, several ferrocene–naphthoquinone dyads were designed to study the factors influencing the ET process [ 13 ]. In addition, ferrocene–naphthalimide–piperazine triads have been shown to allow simultaneous pH and redox sensing [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Electrochemical and Fluorescence Properties of the First Fluorescent Member of the Ferrocifen Family and of Its Oxidized Derivatives

et al. 2022

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The first fluorescent ferrociphenol derivative (P797) has been synthesized via McMurry cross-coupling followed by copper-catalyzed [3 + 2] azide-alkyne cycloaddition of the fluorescent group coumarin. Cyclic voltammograms of P797 exhibit either a monoelectronic oxidation wave ascribed to the ferrocene Fe(II) → Fe(III) conversion or a three-electron oxidation process in the presence of a base, leading to a Fe(III) quinone methide adduct. This general sequence is consistent with those previously described for non-fluorescent ferrociphenols. Furthermore, the fluorescence properties of P797 and its oxidized intermediates appear to strongly depend on the redox state of the ferrocene group. Indeed, electrochemical generation of Fe(III) (ferrocenium) states markedly increases the fluorescence emission intensity. In contrast, the emission of the Fe(II) (ferrocene) states is partially quenched by photoinduced electron transfer (PET) from the Fe(II) donor to the coumarin acceptor and by concentration-dependent self-quenching. Owing to its switchable fluorescence properties, complex P797 could represent an innovative and useful tool to study the biodistribution and the redox state of ferrocifens in cancer cells.

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“…[43][44][45][46][47][48][49] Z. Zhao et al [50] used 1,1'bis(sulfonate)-ferrocene dianion disodium salt pared with the anthraquinone-2,7-disulfonic acid disodium salt; on the other hand, ferrocene decomposed under the acidic conditions used to stabilize the anthraquinone. [42] Considering our expertise in synthesis and applications of electro-active molecules, in particular metallocenes, [51][52][53][54] we synthesized in this work the 1,1'-bis(sulfonate)-ferrocene dianion disodium salt (DSÀ Fc) and two viologen-derivatives, as catholyte and anolyte, respectively, to produce a sustainable neutral-pH AORFB. The performances of the synthesized electrolytes were evaluated in terms of solubility, degradation capacity, retention, and electrical power generation.…”

Section: Introductionmentioning

confidence: 99%

A Neutral‐pH Aqueous Redox Flow Battery Based on Sustainable Organic Electrolytes

et al. 2022

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Aqueous organic redox flow batteries (AORFBs) have gained increasing attention for large-scale storage due to the advantages of decoupled energy and power, safe and sustainable chemistry, and tunability of the redox-active species. Here, we report the development of a neutral-pH AORFB assembled with a highly water-soluble ferrocene 1,1-disulfonic disodium salt (DSÀ Fc) and two viologen derivatives, 1,1'-bis(3-sulfonatopropyl)-viologen (BSPÀ Vi) and Bis(3-trimethylammonium)propyl viologen tetrachloride (BTMAPÀ Vi). Synthesized electrolytes showed excellent redox potential, good diffusion coefficient, and a good transfer rate constant. In particular, BSPÀ Vi has a more negative redox potential (-0.4 V) than BTMAPÀ Vi (À 0.3 V) and faster kinetics; therefore, it was selected to be assembled in an AORFB as anolyte, coupled with DSÀ Fc as catholyte.The resulting AORFB based on BTMAPÀ Vi/DSÀ Fc and BSPÀ Vi/DSÀ Fc redox couple had a high cell voltage (1.2 V and 1.3 V, respectively) and theoretical energy density (13 WhL À 1 and 14 WhL À 1 respectively) and was able to sustain 70 chargedischarge cycles with energy efficiency as high as 97 %.

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Modulating electron transfer in ferrocene-naphthoquinone dyads: New insights in parameters influencing ET efficiency

Cited by 7 publications

References 39 publications

Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study

Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study

Synthesis, Electrochemical and Fluorescence Properties of the First Fluorescent Member of the Ferrocifen Family and of Its Oxidized Derivatives

A Neutral‐pH Aqueous Redox Flow Battery Based on Sustainable Organic Electrolytes

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