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The anti-aromatic dianion and aromatic tetraanion of [18]annulene

Abstract:
π-Conjugated macrocycles behave differently from analogous linear chains because their electronic wavefunctions resemble a quantum particle on a ring, leading to aromaticity or anti-aromaticity. [18]Annulene, (CH)18, is the archetypal non-benzenoid aromatic hydrocarbon. Molecules with circuits of 4n + 2 π electrons, such as [18]annulene (n = 4), are aromatic, with enhanced stability and diatropic ring currents (magnetic shielding inside the ring), whereas those with 4n π electrons, such as the dianion of [18]annulene, are expected to be anti-aromatic and exhibit the opposite behaviour. Here we use 1H NMR spectroscopy to re-evaluate the structure of the [18]annulene dianion. We also show that it can be reduced further to an aromatic tetraanion, which has the same shape as the dianion. The crystal structure of the tetraanion lithium salt confirms its geometry and reveals a metallocene-like sandwich, with five Li+ cations intercalated between two [18]annulene tetraanions. We also report a heteroleptic sandwich, with [18]annulene and corannulene tetraanion decks.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s41557-024-01469-1

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0003-3799-0485
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Role:
Author
ORCID:
0000-0003-0563-0127
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0003-2175-8059
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Role:
Author
ORCID:
0000-0003-4782-021X
More by this author
Role:
Author
ORCID:
0000-0003-0221-7900


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Grant:
885606
Programme:
ARO-MAT


Publisher:
Springer Nature
Journal:
Nature Chemistry More from this journal
Volume:
16
Issue:
6
Pages:
998–1002
Place of publication:
England
Publication date:
2024-03-06
Acceptance date:
2024-02-02
DOI:
EISSN:
1755-4349
ISSN:
1755-4330
Pmid:
38448656


Language:
English
Keywords:
Pubs id:
1776549
Local pid:
pubs:1776549
Deposit date:
2024-06-05
ARK identifier:

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