Molecular assembly (MA) is an essential approach for creating new materials and generating novel functions through a bottom-up strategy based on various non-covalent synergistic interactions. However, the efficiency, controllability, and functionality of current artificial MA systems are far inferior to those in biological systems. It is essential to develop more efficient and controllable strategies. Among the diverse controllable MA methods, catassembly has emerged as a novel concept that utilizes catassemblers to accelerate and control the MA process. Catassembly is an effective approach with high selectivity and precision for enhancing the complexity and functionality of MA systems. The development of catassembly is still in the early stage, making it particularly important to thoroughly and systematically explore its theoretical foundations and framework. Herein, by comparing the concept, nature, and complexity of catassembly with catalysis, we demonstrate the study of catassembly should be categorized based on its complexity from three perspectives: matter, energy, information, and their synergy. Through delving into these unique principles and characteristics that emerged at the different complexity levels of catassembly, we further lay the groundwork physicochemical foundation and theoretical framework for catassembly beyond self-assembly. Firstly, in the dimension of matter, catassembly demonstrates complexity in terms of multi-components, multi-steps, and multi-pathways. We further elucidated the mechanisms of how catassemblers can serve as “constructors” or “transporters” to control product distribution and accelerate the mass transfer process. These catassemblers feature the optimal concentration and binding constants in catassembly processes. Secondly, the non-equilibrium catassembly systems, which are commonly observed in life science, should be investigated in the integrated dimension of energy and matter. Leveraging theories of nonequilibrium thermodynamics and kinetics, we explore how catassemblers mediate energy transfer and maintain these dissipative structures, and how catassemblers facilitate faster achievement of steady states and control the concentration and lifespan of dissipative structures in non-equilibrium catassembly processes. Finally, for complex dynamic functional catassembly systems, the information dimension is incorporated atop the matter-energy dimension. Inspired by information theory, we demonstrate how catassemblers act as information carriers to control MA processes. In addition, we further discuss how catassemblers mediate signal transmission and quantify the channel capacity of signaling pathways. Furthermore, incorporating concepts from control theory, we reveal catassemblers may serve as “regulators” to mediate the synergy of positive and negative feedback, therefore controlling the robustness and functionality of chemical information networks. A clearer theoretical foundation and framework for catassembly study can be established from these three integrating dimensions of matter, energy, and information. Nevertheless, developing the theoretical framework of catassembly is challenging and requires drawing on advanced concepts and methodologies from multiple disciplines and fields, including artificial intelligence. These endeavors will facilitate the development of MA and material science.

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.