Počet záznamů: 1
On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence
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SYSNO ASEP 0549128 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence Tvůrce(i) Gosset, A. (FR)
Nováková Lachmanová, Štěpánka (UFCH-W) ORCID, RID
Cherraben, S. (FR)
Bertho, G. (FR)
Forte, J. (FR)
Perruchot, Ch. (FR)
de Rouville, H.-P. J. (FR)
Pospíšil, Lubomír (UFCH-W) RID, ORCID
Hromadová, Magdaléna (UFCH-W) RID, ORCID, SAI
Bremond, E. (FR)
Lainé, P. P. (FR)Zdroj.dok. Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 27, č. 71 (2021), s. 17889-17899Poč.str. 11 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova potential sweep voltammetry ; charge-transfer ; redox ; chemistry ; electrochemistry ; serendipity ; complexity ; pyridinium ; parameters ; transfers ; electronic structure ; electrostatic interactions ; pyridinium ; structure-activity relationships ; supramolecular electrochemistry Vědní obor RIV CG - Elektrochemie Obor OECD Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) CEP GA21-13458S GA ČR - Grantová agentura ČR 8J21FR016 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Způsob publikování Omezený přístup Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000722147600001 EID SCOPUS 85120647492 DOI 10.1002/chem.202103136 Anotace The synergistic functioning of redox-active components that emerges from prototypical 2,2 '-di(N-methylpyrid-4-ylium)-1,1 '-biphenyl is described. Interestingly, even if a trans conformation of the native assembly is expected, due to electrostatic repulsion between cationic pyridinium units, we demonstrate that cis conformation is equally energy-stabilized on account of a peculiar LUMO (SupLUMO) that develops through space, encompassing the two pyridiniums in a single, made-in-one-piece, electronic entity (superelectrophoric behavior). This SupLUMO emergence, with the cis species as superelectrophore embodiment, originates in a sudden change of electronic structure. This finding is substantiated by insights from solid state (single-crystal X-ray diffraction) and solution (NOE NMR and UV-vis-NIR spectroelectrochemistry) studies, combined with electronic structure computations. Electrochemistry shows that electron transfers are so strongly correlated that two-electron reduction manifests itself as a single-step process with a large potential inversion consistent with inner creation of a carbon-carbon bond (digital simulation). Besides, absence of reductive formation of dimers is a further indication of a preferential intramolecular reactivity determined by the SupLUMO interaction (cis isomer pre-organization). The redox-gated covalent bond, serving as electron reservoir, was studied via atropisomerism of the reduction product (VT NMR study). The overall picture derived from this in-depth study of 2,2 '-di(N-methylpyrid-4-ylium)-1,1 '-biphenyl proves that trans and cis species are worth considered as intrinsically sharply different, that is, as doubly-electrophoric and singly-superelectrophoric switchable assemblies, beyond conformational isomerism. Most importantly, the through-space-mediated SupLUMO may come in complement of other weak interactions encountered in Supramolecular Chemistry as a tool for the design of electroactive architectures. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2022 Elektronická adresa http://hdl.handle.net/11104/0325145
Počet záznamů: 1