On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence.
electronic structure
electrostatic interactions
pyridinium
structure-activity relationships
supramolecular electrochemistry
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
20 Dec 2021
20 Dec 2021
Historique:
received:
27
08
2021
pubmed:
12
11
2021
medline:
22
12
2021
entrez:
11
11
2021
Statut:
ppublish
Résumé
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.
Identifiants
pubmed: 34761431
doi: 10.1002/chem.202103136
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
17889-17899Subventions
Organisme : Agency of the Czech Republic
ID : 21-13458S
Organisme : Academy of Sciences of the Czech Republic
ID : 61388955, 61388963
Organisme : Ministry of Education of the Czech Republic
ID : Barrande Project 8J21FR016
Organisme : French Ministries of Europe and Foreign Affairs (MAE) and of Advanced Education, Research and Innovation (MESRI)
ID : PHC Barrande, 2021 Project No. 46775VG
Organisme : Agence Nationale de la Recherche
ID : "E-StorIc" Project: ANR-14-CE05-0002
Organisme : Grand Équipement National De Calcul Intensif
ID : A0060810359 and A0080810359
Informations de copyright
© 2021 Wiley-VCH GmbH.
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