Determining the absolute configuration of chiral molecules is of fundamental importance in the fields of natural products chemistry, asymmetric catalysis, and pharmaceutical development. A widely adopted approach involves the comparison of experimental and theoretical electronic circular dichroism (ECD) spectra, which has proven to be a reliable method for absolute configuration assignment. However, the generation of theoretical ECD spectra via time-dependent density functional theory (TD-DFT) remains the rate-limiting step in this workflow, making its acceleration both essential and challenging. Although recent advances in deep learning offer promising strategies for establishing structure-spectrum relationships and expediting theoretical spectrum prediction, the lack of standardized and comprehensive ECD spectral datasets continues to hinder progress. This study presents the Chiral Molecular Circular Dichroism Spectral (CMCDS) dataset, a systematically structural benchmark dataset that addresses the fragmentation of existing ECD data. Characterized by high standardization, scalability, and broad molecular diversity, CMCDS facilitates deep learning applications in ECD analysis and fosters data-driven discovery of chiral molecules.

The rational design of chiral fluorescent organic molecular cages requires a comprehensive understanding of structure–activity relationships. In this study, we constructed two molecular face-rotating polyhedra (FRP), namely, FRT-3 and FRT-4, from flexible tris(2-aminoethyl)amine (TREN), rigid Tri-NH2, and tris(4-phenyl)aniline (TFPA). FRT-3 crystallized as a pair of enantiomers (homodirectional, 4M and 4P), while FRT-4 formed three diastereomers (heterodirectional: 3M1P, 3P1M, and 2M2P). To elucidate the effect of vertex geometry on photophysical behavior, we investigated their fluorescence properties in solvents of varying polarities and under protonation. Both FRT-3 and FRT-4 exhibit pronounced intramolecular charge transfer (ICT) behavior and show distinct responses to acids in solution. These findings offer valuable insights into the potential of chiral fluorescent molecular cages for sensing and optoelectronic applications.

The complexity of multi-component molecular assembly demands precise control strategies to enhance both efficiency and selectivity. Heterogeneous nucleation and the autocatalytic secondary pathway, as key regulatory strategies, have attracted widespread attention for their crucial roles in crystal growth and amyloid protein aggregation. Here, we apply a heterogeneous nucleation strategy to supramolecular polymer systems and report the first direct observation of surface-enrichment-induced primary nucleation and a spontaneous fragmentation-driven autocatalytic secondary process. A heterogeneous nucleating agent promotes primary nucleation, facilitating supramolecular chiral induction. The resulting chiral polymers undergo a catalytic cycle of fragmentation and re-growth at their termini, with the fragments also acting as seeds for nucleation and growth. These pathways play a crucial role in the polymerization process and are essential for chiral transfer and asymmetry amplification, enabling the achievement of maximum enantioselectivity with as little as 0.5% molar equivalent of the heterogeneous nucleating agent. Furthermore, we reveal the existence of an optimal equivalent in their catalytic kinetics, arising from a surface assembly mechanism. In this mechanism, monomers adsorbed on the surface of the heterogeneous nucleating agent assemble with those in solution, rather than through surface diffusion and assembly. This process resembles the surface-catalyzed Eley–Rideal mechanism. Our study highlights the potential of heterogeneous nucleation as an effective strategy for controlling supramolecular polymerization and offers new insights into its underlying mechanism.

The assembly of peptides is generally mediated by liquid–liquid phase separation, which enables control over assembly kinetics, final structure, and functions of peptide-based supramolecular materials. Modulating phase separation can alter the assembly kinetics of peptides by changing solvents or introducing external fields. Herein, we demonstrate that the assembly of peptides can be effectively catalyzed by complex coacervates. The negatively charged sodium alginate (SA) can form complex coacervates with the positively charged KLVFFAE (Aβ16–22, abbreviated as KE) peptide, thereby lowering the nucleation barrier and promoting the assembly of the peptide. As the binding affinity of SA-KE and the dosage of SA decrease, the system shifts from a relatively inefficient template-induced assembly to a highly efficient catalytic assembly before ultimately reverting to slow spontaneous assembly. Therefore, both the affinity as well as the stoichiometry do not follow the intuitive rule that “more is better”, but rather there exists an optimal value that maximizes the rate of assembly.