2021
DOI: 10.26434/chemrxiv.14035919.v1
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How Aromatic Are Molecular Nanorings? The Case of a Six-Porphyrin Nanoring

Abstract: <div> <div> <div> <p>Large conjugated rings give rise to novel promising structures that can sustain persistent currents at low temperatures even in the presence of strong magnetic fields. One of the most interesting such molecules was recently synthesized [Anderson et al., Nature, 2017, 541, 3512] in the form of a six-porphyrin nanoring structure, which, according to the authors, in its +6-oxidation state (c-P66+) sustained an aromatic ring current involving 78π electrons; … Show more

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Cited by 3 publications
(6 citation statements)
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“…B3LYP usually gives the lowest average electron numbers in the NNA basins, the largest zero-electron probabilities, and the lowest oxidation states. This result is in line with the large delocalization errors documented in conjugated and aromatic molecules. , CAM-B3LYP and M06-2X do not suffer from large delocalization errors and often provide similar NNA electron numbers, although slightly lower than those given by MP2. On the other hand, HF, which tends to overestimate electron localization, provides the largest electron numbers in the NNA basin.…”
Section: Discussionsupporting
confidence: 81%
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“…B3LYP usually gives the lowest average electron numbers in the NNA basins, the largest zero-electron probabilities, and the lowest oxidation states. This result is in line with the large delocalization errors documented in conjugated and aromatic molecules. , CAM-B3LYP and M06-2X do not suffer from large delocalization errors and often provide similar NNA electron numbers, although slightly lower than those given by MP2. On the other hand, HF, which tends to overestimate electron localization, provides the largest electron numbers in the NNA basin.…”
Section: Discussionsupporting
confidence: 81%
“…All structures were optimized at the CAM-B3LYP/ma-TZVP , level of theory. It has been recently documented that this functional avoids large delocalization errors, which could give rise to spurious critical points in the potential energy surface. , For these optimized geometries, single-point calculations with various basis sets and density functional approximations (CAM-B3LYP, B3LYP, , M06-2X, and MN15) as well as Hartree–Fock (HF) and MP2 methods have been performed. Although HF completely neglects electron correlation and, in most cases, density functional approximations (DFAs) provide more accurate energies and geometries, DFAs struggle to reproduce the electron density of some electrides with unpaired electrons.…”
Section: Methodsmentioning
confidence: 99%
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“…In this regard, we note that we deliberately chose the CAM-B3LYP functional, which has been shown not to suffer from overdelocalization errors; 90,91 such errors could lead to spurious results, including exaggerated planarity and over-estimation of aromatic stabilization. Nevertheless, to try to pinpoint the source of the discrepancy, we studied the relationship between the size of the molecule and the difference in relative energy, ∆E rel = E rel (DFT) − E rel (xTB).…”
Section: The Relative Energymentioning
confidence: 99%
“…Aromaticity is one of the most longstanding concepts in physical organic chemistry, yet in many cases the assignment of a molecule as "aromatic" or "antiaromatic" elicits heated debate, [1][2][3] especially as a molecule's structure strays further from that of the archetype aromatic, benzene.…”
Section: Toc Graphicsmentioning
confidence: 99%