Publication details

How Does a Container Affect Acidity of its Content? Charge-Depletion Bonding Inside Fullerenes

Authors

JAROŠ Adam BADRI Zahra BORA Pankaj Lochan FARAJPOUR BONAB Esmaeil MAREK Radek STRAKA Michal FOROUTANNEJAD Cina

Year of publication 2018
Type Article in Periodical
Magazine / Source Chemistry - A European Journal
MU Faculty or unit

Central European Institute of Technology

Citation
Web DOI: 10.1002/chem.201706017
Doi http://dx.doi.org/10.1002/chem.201706017
Keywords bonding; fullerene; lone-pair-pi; cage; bonding analysis
Attached files
Description A recent study (Sci. Adv. 2017, 3, e1602833) has shown that FH...OH2 hydrogen bond in a HF·H2O pair substantially shortens and the H-F bond elongates upon encapsulation of the cluster in C70 fullerene. This has been attributed to compression of the HF·H2O pair inside the cavity of C70. Here we present theoretical evidence that the effect is not caused by a mere compression of the H2O·HF pair but it is related to a strong lone-pair-pi (LP-pi) bonding with the fullerene cage. To support this argument, a systematic electronic structure study of selected small molecules (HF, H2O, and NH3) and their pairs enclosed in fullerene cages (C60, C70, and C90) has been performed. Bonding analysis revealed unique LP-picage interactions with a charge-depletion character in the bonding region, unlike usual LP-pi bonds. The LP-picage interactions were found to be responsible for elongation of the H-F bond. Thus, the HF appears to be more acidic inside the cage. The shortening of the FH…OH2 contact in (HF·H2O)@C70 originates from an increased acidity of the HF inside the fullerenes. Such trends are also observed in other studied systems.
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