Global aromaticity at the nanoscale.
Journal
Nature chemistry
ISSN: 1755-4349
Titre abrégé: Nat Chem
Pays: England
ID NLM: 101499734
Informations de publication
Date de publication:
03 2020
03 2020
Historique:
received:
26
06
2019
accepted:
20
11
2019
pubmed:
22
1
2020
medline:
22
1
2020
entrez:
22
1
2020
Statut:
ppublish
Résumé
Aromaticity can be defined by the ability of a molecule to sustain a ring current when placed in a magnetic field. Hückel's rule states that molecular rings with [4n + 2] π-electrons are aromatic, with an induced magnetization that opposes the external field inside the ring, whereas those with 4n π-electrons are antiaromatic, with the opposite magnetization. This rule reliably predicts the behaviour of small molecules, typically with fewer than 22 π-electrons (n = 5). It is not clear whether aromaticity has a size limit, or whether Hückel's rule extends to much larger macrocycles. Here, we present evidence for global aromaticity in porphyrin nanorings with circuits of up to 162 π-electrons (n = 40); aromaticity is controlled by changing the constitution, oxidation state and conformation. Whenever a ring current is observed, its direction is correctly predicted by Hückel's rule. The largest ring currents occur when the porphyrin units have fractional oxidation states.
Identifiants
pubmed: 31959963
doi: 10.1038/s41557-019-0398-3
pii: 10.1038/s41557-019-0398-3
pmc: PMC7049293
mid: EMS85001
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
236-241Subventions
Organisme : European Research Council
ID : 320969
Pays : International
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