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Intra-host π-π interactions in crown ether complexes revealed by cryogenic ion mobility-mass spectrometry.
Physical Chemistry Chemical Physics : PCCP 2024 April 16
Cryogenic ion mobility-mass spectrometry was performed to investigate the relative abundance of conformers of dinaphtho-24-crown-8 (DN24C8) complexes with alkali metal cations M+ (M = Li, Na, K, Rb, and Cs). The "closed" conformers of M+ (DN24C8) with short distances between two naphthalene rings in the crown ethers were predominantly observed for all complexes at 86 K. The two noncovalent interactions, host-guest and intra-host interactions, were analyzed separately by density functional theory calculations to reveal the origin of the stability of the closed conformers. As a result, it was revealed that the intra-host π-π interactions have a more critical role in determining the stability of the conformers than the host-guest interactions. The closed conformers of M+ (DN24C8) also have wider regions of the π-π interactions than those of the M+ (dibenzo-24-crown-8) complexes.
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