A Foldable Cyclic Oligomer: Chiroptical Modulation through Molecular Folding upon Complexation and a Change in Temperature

Abstract

A foldable cyclic oligomer <b>1</b> consisting of three terephthalamide units spaced with a 3-fold <i>o</i>-phenylene unit presented a dynamic pair of enantiomeric forms through molecular folding, to which the external chirality on a ditopic guest [(<i>S</i>,<i>S</i>)-<b>2</b> or (<i>R</i>,<i>R</i>)-<b>2</b>] was supramolecularly transferred to prefer a particular sense of dynamic helicity [(<i>M</i>,<i>M</i>)-/(<i>P</i>,<i>P</i>)-<b>1</b> and (<i>M</i>,<i>M</i>,<i>P</i>)-/(<i>P</i>,<i>P</i>,<i>M</i>)-<b>1</b>]. In the macrocycle, the terephthalamide units acted as exotopic binding sites to fold into helical forms upon complexation. The internal chirality associated with a host [(<i>R</i>,<i>R</i>,<i>R</i>,<i>R</i>,<i>R</i>,<i>R</i>)-<b>1b</b>] had no preference in a helical sense in the absence of a guest. Instead, the internal chirality was responsible for the signal modulation that it was cooperatively or competitively transferred in response to the external chirality on a guest (<i>S</i>,<i>S</i>)-<b>2</b> or (<i>R</i>,<i>R</i>)-<b>2</b>. During the diastereomeric complexation, a particular sense of dynamic helicity was favored due to cooperative transmission of chirality when the helical preference was matched between the host and guest. Alternatively, the host complexed with an antipodal guest underwent a drastic change in conformation upon a change in temperature