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The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[ n ]urils with Uncharged Polar Guests

Grimm, Laura M. 1; Spicher, Sebastian; Tkachenko, Boryslav; Schreiner, Peter R. ; Grimme, Stefan ; Biedermann, Frank 1
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)


The rationalization of non-covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host-guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (ΔG, ΔH, TΔS) for CB7 and CB8 with a set of hydroxylated adamantanes, di-, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high-level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity-controlling factors for CBn complexes. In contrast, peculiar host-related solvation effects were identified as the major factor for rationalizing the unique behavior and record-affinity characteristics of cucurbit[n]urils.

Verlagsausgabe §
DOI: 10.5445/IR/1000146953
Veröffentlicht am 02.06.2022
DOI: 10.1002/chem.202200529
Zitationen: 11
Web of Science
Zitationen: 13
Zitationen: 12
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2022
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000146953
HGF-Programm 43.31.02 (POF IV, LK 01) Devices and Applications
Erschienen in Chemistry – A European Journal
Verlag John Wiley and Sons
Band 28
Heft 38
Seiten e202200529
Vorab online veröffentlicht am 25.05.2022
Nachgewiesen in Web of Science
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