Počet záznamů: 1
Solvent-controlled formation of alkali and alkali-earth-secured cucurbituril/guest trimers
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SYSNO ASEP 0575698 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Solvent-controlled formation of alkali and alkali-earth-secured cucurbituril/guest trimers Tvůrce(i) Lončarić, Doroteja (UOCHB-X)
Movahedifar, F. (US)
Štoček, Jakub Radek (UOCHB-X) ORCID
Dračínský, Martin (UOCHB-X) RID, ORCID
Cvačka, Josef (UOCHB-X) RID, ORCID
Guan, S. (US)
Bythell, B. J. (US)
Císařová, I. (CZ)
Masson, E. (US)
Kaleta, Jiří (UOCHB-X) RID, ORCIDZdroj.dok. Chemical Science . - : Royal Society of Chemistry - ISSN 2041-6520
Roč. 14, č. 35 (2023), s. 9258-9266Poč.str. 9 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova solvation free-energies ; crystal structures ; model Obor OECD Organic chemistry CEP GA20-13745S GA ČR - Grantová agentura ČR LTAUSA19120 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Způsob publikování Open access Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 001167938200001 EID SCOPUS 85170240590 DOI 10.1039/d3sc02032k Anotace Cucurbit[7]uril (CB[7]) encapsulates adamantyl and trimethylsilyl substituents of positively charged guests in dimethyl sulfoxide (DMSO). Unlike in water or deuterium oxide, addition of a selection of alkali and alkali-earth cations with van der Waals radii between 1.0 and 1.4 Å (Na+, K+, Ca2+, Sr2+, Ba2+ and Eu3+) to the CB[7]/guest complexes triggers their cation-mediated trimerization, a process that is very slow on the nuclear magnetic resonance (NMR) time scale. Smaller (Li+, Mg2+) or larger cations (Rb+, Cs+ or NH4+) are inert. The trimers display extensive CH-O interactions between the equatorial and pseudo-equatorial hydrogens of CB[7] and the carbonyl rim of the neighboring CB[7] unit in the trimer, and a deeply nested cation between the three interacting carbonylated CB[7] rims, a counteranion is likely perched in the shallow cavity formed by the three outer walls of CB[7] in the trimer. Remarkably, a guest must occupy the cavity of CB[7] for trimerization to take place. Using a combination of semi-empirical and density functional theory techniques in conjunction with continuum solvation models, we showed that trimerization is favored in DMSO, and not in water, because the penalty for the partial desolvation of three of the six CB[7] portals upon aggregation into a trimer is less unfavorable in DMSO compared to water. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2024 Elektronická adresa https://doi.org/10.1039/D3SC02032K
Počet záznamů: 1