Supramolecular Chirality Issues in Unorthodox Naphthalene Diimide Gelators

Abstract

Herein, the self-assembly of a few 1,3-dihydroxyl functionalized naphthalene diimide (NDI) derivatives has been reported with particular emphasis on the impact of chirality on gelation and the effect of self-assembly on charge-carrier mobility. A nonconventional gelator (R)-NDI, devoid of any long alkyl chains, exhibited spontaneous gelation in tetra-chloroethylene (TCE). Based on X-ray crystallography and powder X-ray diffraction studies, it was established that a ladder-like hydrogen-bonded chain formation between the 1,3-dihydroxyl group leads to the fibrillar structures with preferential helicity. Likewise the (S)-isomer also exhibited identical gelation and mesoscopic structure but produced fibrils with the opposite handedness. Intriguingly, an equimolar mixture of the (R)- and (S)-isomers did not show any gelation ability, rather a macroscopic precipitation was observed and, in sharp contrast to the individual isomers, the morphology of the mixture showed ill-defined near spherical agglomerates. Differential scanning calorimetry (DSC) studies revealed an identical crystallization peak for the supramolecular polymer produced from the enantiopure gelators ((R)- or (S)-isomer), which was absent in their equimolar mixture. However, mixtures of the two isomers with enantiomeric excess retrieved the gelation ability and preferential helicity demonstrating that chiral amplification is operative in the present system through the so-called “majority rule” effect. Chirality induction was also realized by the “sergeant and soldier” principle in the supramolecular assembly of an achiral NDI gelator in the presence of either the (R)- or (S)-isomer as the chiral dopant. However, the strong helical bias induced by the chiral gelator was found to be opposite in nature compared to that found in the self-assembly of the pure chiral gelator that has been rarely reported in the literature. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements indicated the strong positive impact of the gelation on the electrical conductivity.