Close Stacking of Antiaromatic Ni(II) Norcorrole Originating from a Four-Electron Multicentered Bonding Interaction.
J Am Chem Soc
; 146(13): 9311-9317, 2024 Apr 03.
Article
em En
| MEDLINE
| ID: mdl-38502926
ABSTRACT
A π-conjugated molecule with one electronic spin often forms a π-stacked dimer through molecular orbital interactions between two unpaired electrons. The bonding is recognized as a multicentered two-electron interaction between the two π-conjugated molecules. Here, we disclose a multicentered bonding interaction between two antiaromatic molecules involving four electrons. We have synthesized an antiaromatic porphyrin analogue, Ni(II) bis(pentafluorophenyl)norcorrole. Its dimer adopts a face-to-face stacked structure with an extremely short stacking distance of 2.97 Å. The close stacking originates from a multicenter four-electron bonding interaction between the two molecules. The bonding electrons were experimentally observed via synchrotron X-ray diffraction analysis and corroborated by theoretical calculations. The intermolecular interaction of the molecular orbitals imparts the stacked dimer with aromatic character that is distinctly different from that of its monomer.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Japão