A New Class of Hydroxy-Substituted Squaraine Rotaxane

Abstract

A templated macrocyclization reaction was used to permanently encapsulate a highly fluorescent hydroxy-substituted squaraine dye inside a tetralactam macrocycle. The free squaraine dye is quite rigid due to internal hydrogen bonding and its photophysical properties hardly change upon encapsulation. A combination of X-ray and NMR data show that the surrounding tetralactam macrocycle adopts an unusually rigid chair conformation and does not undergo rapid pirouetting. Because of its large size and conformational rigidity, the macrocycle creates anisotropic NMR shielding zones that extend over the N,N-dibutylamino groups at each end of the squaraine thread. This shielding anisotropy allows hindered aryl-N rotation to be observed by NMR spectroscopy and provides direct experimental evidence that quinoid-like resonance structures are major contributors to the bis(N,N-dialkylaminophenyl)squaraine resonance hybrid.