Direct Through-Space Substituent-π Interactions in Noncovalent Arene-Fullerene Assemblies.

Autor: Hashikawa Y; Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan., Murata Y; Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2024 Apr 16; Vol. 19 (8), pp. e202400075. Date of Electronic Publication: 2024 Mar 07.
DOI: 10.1002/asia.202400075
Abstrakt: The arene-arene interactions between electron-rich and deficient aromatics have been less understood. Herein, we focus on a [60]fullerene π-surface as an electron-deficient aromatics. Using a 1 H signal of H 2 O@C 60 as a magnetic probe, the presence of benzene-fullerene interactions was confirmed. To investigate substituent effects on the noncovalent arene-fullerene interactions, NMR titration experiments were carried out using an open-[60]fullerene and a series of substituted benzenes, i. e., PhX (X=NO 2 , CN, Cl, OMe, H, CH 3 , and NH 2 ), demonstrating a 1 : 2 stoichiometry with a positive correlation between stabilization energies upon the first association (ΔG 1 ) and Hammet constants (σ m ). The destabilization of the self-assembled structure for X=OMe with a σ-withdrawing nature clearly showed direct through-space substituent-π interactions describable by the Wheeler-Houk model while the second association was suggested to be considerably perturbed by the secondary effects.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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