Ether Naphthotube Host-Guest Complexes and [2]Rotaxanes with Dications

The interactions between ether naphthotube and a series of dication guests in organic solution were investigated. It was found that ether naphthotube formed stable host-guest complexes selectively with these guests in a 1 : 1 stoichiometric ratio with association constants ranging from 102 to 106 M-1, which were confirmed by 1H-NMR spectra and ITC experiments. The host-guest interactions are driven by enthalpy change as the entropic factors are unfavorable. Positive correlations between Delta H and Delta S have been observed in the host-guest complexes. Furthermore, the para-substitution of the guests can significantly affect the binding affinities through a combination of field/inductive and resonance effects by following a linear free energy relationship. Based on the host-guest complexes composed of ether naphthotube and organic cations, two interlocked [2]rotaxanes were prepared by cationization reaction and Huisgen cycloaddition between the cations and the stopper components. The ether naphthotube-based host-guest complexes are useful for creating sophisticated interlocked molecules. Ether naphthotube was able to complex strongly with organic dications in organic solution to give an association constant up to 106 M-1. Thermodynamically, the host-guest interactions are exclusively enthalpically driven and enthalpy-entropy compensation phenomena have been observed. Besides, a linear free energy correlation was observed between binding strengths and the Hammett substituent constants. The host-guest system can be directly applied for the preparation of more complex interlocked molecules by simple stoppering. image