A complete study of the through-the-annulus threading of the larger calix[8]arene macrocycle with di-n-alkylammonium cations has been performed in the presence of the “superweak” TFPB counterion. Thus, it was found that such threading occurs only upon partial preorganization of the calix[8]arene macroring by intramolecular bridging. In particular, 1,5-bridged calix[8]arenes with a meta- or para-xylylene bridge (2 and 3) gave pseudo[2]rotaxanes in which one dialkylammonium axle (4a−4e+) was threaded into one of the two subcavities of the calix[8]-wheel. Conformational studies by using chemical shift surface maps and DFT calculations evidenced a 3/4-cone geometry for these subcavities. Higher pseudorotaxane Kass values were obtained for calix[8]-wheels 2 and 3, with respect to calix[6]-host 1a, due to the cooperative effect of their two subcavities. Dynamic NMR studies on calix[8]-pseudorotaxanes evidenced a direct correlation between Kass (and ΔGass) values and energy barriers for calix inversion due to the effectiveness of thread templation. In accordance with DFT calculations, an endo-alkyl preference, over the endo-benzyl one, was observed by threading calix[8]-wheel 3 with the directional n-butylbenzylammonium axle 4d+.

Through-the-Annulus Threading of the Larger Calix[8]arene Macrocycle

GAETA, CARMINE;TALOTTA, CARMEN;MARGARUCCI, LUIGI;CASAPULLO, Agostino;NERI, Placido
2013-01-01

Abstract

A complete study of the through-the-annulus threading of the larger calix[8]arene macrocycle with di-n-alkylammonium cations has been performed in the presence of the “superweak” TFPB counterion. Thus, it was found that such threading occurs only upon partial preorganization of the calix[8]arene macroring by intramolecular bridging. In particular, 1,5-bridged calix[8]arenes with a meta- or para-xylylene bridge (2 and 3) gave pseudo[2]rotaxanes in which one dialkylammonium axle (4a−4e+) was threaded into one of the two subcavities of the calix[8]-wheel. Conformational studies by using chemical shift surface maps and DFT calculations evidenced a 3/4-cone geometry for these subcavities. Higher pseudorotaxane Kass values were obtained for calix[8]-wheels 2 and 3, with respect to calix[6]-host 1a, due to the cooperative effect of their two subcavities. Dynamic NMR studies on calix[8]-pseudorotaxanes evidenced a direct correlation between Kass (and ΔGass) values and energy barriers for calix inversion due to the effectiveness of thread templation. In accordance with DFT calculations, an endo-alkyl preference, over the endo-benzyl one, was observed by threading calix[8]-wheel 3 with the directional n-butylbenzylammonium axle 4d+.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/4017070
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