Chiral cage compounds are mainly constructed from chiral precursors or based on the symmetry breaking during coordination-driven self-assembly. Herein, we present a strategy to construct chiral organic cages by restricting the P or M rotational configuration of tetraphenylethylene (TPE) faces through dynamic covalent chemistry. The combination of graph theory, experimental characterizations and theoretical calculations suggests emergent chirality of cages is originated from complex arrangements of TPE faces with different orientational and rotational configurations. Accompanied by the generation of chirality, strong fluorescence also emerged during cage formation, even in dilute solutions with various solvents. In addition, the circularly polarized luminescence of the cages is realized as a synergy of their dual chiral and fluorescence properties. Chirality and fluorescence of cages are remarkably stable, because intramolecular flipping of phenyl rings in TPE faces is restricted, as indicated by calculations. This study provides insight into construct chiral cages by the rational design through graph theory, and might facilitate further design of cages and other supramolecular assemblies from aggregation-induced emission active building blocks.
In nature, protein subunits on the capsids of many icosahedral viruses form rotational patterns, and mathematicians also incorporate asymmetric patterns into faces of polyhedra. Chemists have constructed molecular polyhedra with vacant or highly symmetric faces, but very little is known about constructing polyhedra with asymmetric faces. Here we report a strategy to embellish a C3h truxene unit with rotational patterns into the faces of an octahedron, forming chiral octahedra that exhibit the largest molar ellipticity ever reported, to the best of our knowledge. The directionalities of the facial rotations can be controlled by vertices to achieve identical rotational directionality on each face, resembling the homo-directionality of virus capsids. Investigations of the kinetics and mechanism reveal that non-covalent interaction among the faces is essential to the facial homo-directionality.
Chiral amplification in molecular self-assembly has profound impact on the recognition and separation of chiroptical materials, biomolecules, and pharmaceuticals. An understanding of how to control this phenomenon is nonetheless restricted by the structural complexity in multicomponent self-assembling systems. Here, we create chiral octahedra incorporating a combination of chiral and achiral vertices and show that their discrete nature makes these octahedra an ideal platform for in-depth investigation of chiral transfer. Through the construction of dynamic combinatorial libraries, the unique possibility to separate and characterise each individual assembly type, density functional theory calculations, and a theoretical equilibrium model, we elucidate that a single chiral unit suffices to control all other units in an octahedron and how this local amplification combined with the distribution of distinct assembly types culminates in the observed overall chiral amplification in the system. Our combined experimental and theoretical strategy can be applied generally to quantify discrete multi-component self-assembling systems.
Chiral organic cages can assist enantio-selective supramolecular polymerization through a catalyzed assembly (catassembly) strategy, like chaperones assist the assembly of biomolecules.
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