Electron Storage System Based on a Two-Way Inversion of Redox Potentials

Autor: Ilaria Ciofini, Fabien Tuyèras, Magdaléna Hromadová, Štěpánka Nováková Lachmanová, Philippe P. Lainé, Christian Perruchot, Henri-Pierre Jacquot de Rouville, Philippe Ochsenbein, Grégory Dupeyre, Lubomír Pospíšil, Alexis Gosset, Hyacinthe Randriamahazaka, Romana Sokolová, Liam Wilbraham
Přispěvatelé: Université de Paris, Laboratoire ITODYS, CNRS, F-75006 Paris, Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), J. Heyrovský Institute of Physical Chemistry of the ASCR, Czech Academy of Sciences [Prague] (CAS), Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sanofi-Aventis R&D, SANOFI Recherche, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Electronique et intelligence artificielle (UR ELAN), Centre national du machinisme agricole, du génie rural, des eaux et forêts (CEMAGREF)
Rok vydání: 2020
Předmět:
Zdroj: Journal of the American Chemical Society
Journal of the American Chemical Society, American Chemical Society, 2020, 142 (11), pp.5162-5176. ⟨10.1021/jacs.9b12762⟩
Journal of the American Chemical Society, American Chemical Society, 2020, ⟨10.1021/jacs.9b12762⟩
ISSN: 1520-5126
0002-7863
Popis: International audience; Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of "structronics" (a neologism derived from "structure" and "electronics"). Through this concept, we establish, synthesize, and thoroughly study two multicomponent "super-electrophores": 1,8-dipyridyliumnaphtha-lene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this "super-LUMO" serves as an empty reservoir, which can be filled by a two-electron reduction, giving rise to an elongated C−C bond or "super-HOMO". Because of its weakened nature, this bond can undergo an electrochemically driven cleavage at a significantly more anodicyet accessiblepotential, thereby restoring the availability of the electron pair (reservoir emptying). In the representative case study of 2, an inversion of potential in both of the two-electron processes of bond formation and bond-cleavage is demonstrated. Overall, the structronic function is characterized by an electrochemical hysteresis and a chemical reversibility. This structronic superelectrophore can be viewed as the three-dimensional counterpart of benchmark methyl viologen (MV).
Databáze: OpenAIRE
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