Slow Intermolecular Complexation–Decomplexation Exchanges of Cyclodextrins in Fullerene and Its Derivative Complexes
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Fullerenes (C60 and C70) and several functionalized C60 derivatives can be encapsulated in two γ-cyclodextrins (γ-CDxs). Although intermolecular complexation–decomplexation exchange of γ-CDx is known to be very slow, the exchange rates have yet to be quantitatively measured. Herein, we determined that the pseudo-firstorder association and dissociation rate constants for the γ-CDx2•C70 complex were 4.3 and 0.6 s−1 at 23℃, respectively. In contrast, the intermolecular exchange rates for the γ-CDx2•C60 and C60 derivative complexes were slower than the time scale of exchange spectroscopy NMR experiments and the exchange rate constants were in the order of 10−4 s−1. Furthermore, a γ-CDx2•C60 derivative complex was shown to have different intermolecular exchange rates for the two γ-CDxs depending on steric hindrance from the substituent on the C60 derivative.
This work was supported by JSPS KAKENHI Grant-in-Aid for Scientific Research (B) (Grant No. JP16H04133) and Grant-in-Aid for Challenging Exploratory Research (Grant No. JP16K13982).
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This is the accepted version of the following article: A. Ikeda, T. Mae, K. Sugikawa, K. Komaguchi, T. Konishi, T. Hirao, and T. Haino, Slow Intermolecular Complexation–Decomplexation Exchanges of Cyclodextrins in Fullerene and Its Derivative Complexes, ChemistrySelect, 2, 11322–11327, 2017, which has been published in final form at http://doi.org/10.1002/slct.201702319. This article may be used for non-commercial purposes in accordance with Wiley Self-Archiving Policy.
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