Architecture-Controllable Single-Crystal Helical Self-assembly of Small-Molecule Disulfides with Dynamic Chirality

Beyond the common supramolecular helical polymers in solutions, controlling single-crystal helical self-assembly with precisely defined chirality and architectures has been challenging. Here, we report that simply merging static homochiral amino acids with dynamic chiral disulfides can produce a class of building blocks featuring supramolecular helical single-crystal self-assembly with unusual stereodivergency. Analysis of 20 single-crystal structures of 1,2-dithiolanes gives an atom-precision understanding of the chirality transfer from the molecular to supramolecular level, featuring homochiral and heterochiral helical supramolecular self-assembly in the solid state. The underlying structure-assembly relationship reveals that the synergistic interplay of intermolecular H-bonds and the 1,2-dithiolane ring with adaptive chirality plays a key role in determining the assembly pathway, also involving the effects of residue groups, substituents, molecular stacking, and solvents. The confinement effect in the solid state can stabilize the dynamic stereochemistry of disulfide bonds and selectively result in specific conformers that can minimize the energy of global supramolecular systems. We envision that these results represent a starting point to use dynamic chiral disulfide as a functional entity in supramolecular chemistry and may inspire a new class of supramolecular helical polymers with dynamic functions.

Automated summary

By merging static homochiral amino acids with dynamic chiral disulfides, a new class of building blocks with supramolecular helical single-crystal self-assembly and unusual stereodivergency is produced. The study provides an atom-precision understanding of chirality transfer from the molecular to the supramolecular level and reveals the mechanisms behind the homochiral and heterochiral helical supramolecular self-assembly in the solid state. These findings open up new possibilities in the field of supramolecular chemistry and may lead to the development of supramolecular helical polymers with dynamic functions.