TY - JOUR
T1 - How Aromatic Are Molecular Nanorings? The Case of a Six-Porphyrin Nanoring**
AU - Casademont-Reig, Irene
AU - Guerrero-Avilés, Raúl
AU - Ramos-Cordoba, Eloy
AU - Torrent-Sucarrat, Miquel
AU - Matito, Eduard
N1 - Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
PY - 2021/11/2
Y1 - 2021/11/2
N2 - Large conjugated rings with persistent currents are novel promising structures in molecular-scale electronics. A six-porphyrin nanoring structure that allegedly sustained an aromatic ring current involving 78π electrons was recently synthesized. We provide here compelling evidence that this molecule is not aromatic, contrary to what was inferred from the analysis of 1H-NMR data and computational calculations that suffer from large delocalization errors. The main reason behind the absence of an aromatic ring current in these nanorings is the low delocalization in the transition from the porphyrins to the bridging butadiyne linkers, which disrupts the overall conjugated circuit. These results highlight the importance of choosing a suitable computational method to study large conjugated molecules and the appropriate aromaticity descriptors to identify the part of the molecule responsible for the loss of aromaticity.
AB - Large conjugated rings with persistent currents are novel promising structures in molecular-scale electronics. A six-porphyrin nanoring structure that allegedly sustained an aromatic ring current involving 78π electrons was recently synthesized. We provide here compelling evidence that this molecule is not aromatic, contrary to what was inferred from the analysis of 1H-NMR data and computational calculations that suffer from large delocalization errors. The main reason behind the absence of an aromatic ring current in these nanorings is the low delocalization in the transition from the porphyrins to the bridging butadiyne linkers, which disrupts the overall conjugated circuit. These results highlight the importance of choosing a suitable computational method to study large conjugated molecules and the appropriate aromaticity descriptors to identify the part of the molecule responsible for the loss of aromaticity.
KW - aromaticity
KW - delocalization error
KW - nanoring
UR - https://www.scopus.com/pages/publications/85112294145
U2 - 10.1002/anie.202108997
DO - 10.1002/anie.202108997
M3 - Article
C2 - 34260804
AN - SCOPUS:85112294145
SN - 1433-7851
VL - 60
SP - 24080
EP - 24088
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 45
ER -