On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00549128" target="_blank" >RIV/61388955:_____/21:00549128 - isvavai.cz</a>

Result on the web

<a href="http://hdl.handle.net/11104/0325145" target="_blank" >http://hdl.handle.net/11104/0325145</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202103136" target="_blank" >10.1002/chem.202103136</a>

Result language

angličtina

Original language name

On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Volume of the periodical

27

Issue of the periodical within the volume

71

Country of publishing house

DE - GERMANY

Number of pages

11

Pages from-to

17889-17899

UT code for WoS article

000722147600001

EID of the result in the Scopus database

2-s2.0-85120647492