Design of Chiral Supramolecular Polymers Exhibiting a Negative Nonlinear Response.

Many synthetic and supramolecular chiral polymeric systems are known to exhibit the "majority rules effect" (MRE), a positive nonlinear response in which a small enantiomeric excess () of the chiral building blocks leads to unproportionally large chiroptical signals near zero . In contrast, the opposite "racemate rules effect" (RRE), a negative nonlinear response in which the chiroptical signals are flat near zero , while giving large nonlinear chiroptical responses to at high values, has only been occasionally observed. The origin of this unusual dependence remains elusive largely because few systems have been established that exhibit this effect. Herein, we present a design approach that enables the development of chiral supramolecular polymers with a pronounced negative nonlinear response akin to RRE. This is achieved by in situ generating a bidentate inducer for supramolecular polymerization that exists in both - and homochiral forms upon reacting with chiral guests. The presence of the -inducer creates an aggregate structure that has a little response in the circular dichroism (CD) spectra as a function of at a particular wavelength, but a homochiral inducer gives large changes in response to at this wavelength. This allowed for an RRE-like response to be observed when the CD intensity of the supramolecular polymers was plotted against the of the chiral guests that generate the - and homochiral inducers without the necessity of the racemic guest preferentially being incorporated into the polymer.