Dynamic covalent component self-sorting processes have been investigated for constituents of dif ferent cyclic orders, macrocycles and macrobicyclic cages based on multiple reversible imine formation. The progressive assembly of the final structures from dialdehyde and polyamine components involved the generation of kinetic products and mixtures of intermediates which underwent component selection and self-correction to generate the final thermodynamic constituents. Importantly, constitutional dynamic networks (CDNs) of macrocycles and macrobicyclic cages were set up either from separately prepared constituents or by in situ assembly from their components. Over time, these CDNs underwent conversion from a kinetically trapped out-of-equilibrium distribution of constituents to the thermodynamically self-sorted one through component exchange in different dimensional orders.

The one-step synthetic strategy for the preparation of the hitherto unknown calix[3]carbazole from readily available starting materials is described. Calix[3]carbazole is obtained in 20% yield, and it could selectively bind the N(C2H5)4(+) cation (tetraethylammonium, TEA) via cation-π interactions. The experimental and modeling results indicate that calix[3]carbazole possesses a larger π-cavity as well as a better chromophoric property than the traditional phenol-based macrocycles, and thus is capable of binding to and optically responding to the relatively large guest TEA.

DNA three-way junctions (TWJ-DNA) are intermediate structures in DNA replication and/or recombination. They play very important roles in biological processes, but more subtle functions are still unknown due partially to the lack of a fluorescent ligand. In this study, a cationic calix[3]carbazole (2) has been synthesized and its properties of interacting with TWJ-DNA have been evaluated by UV/Vis and fluorescence spectroscopy, circular dichroism (CD), gel electrophoresis, and H NMR studies. The results show that 2 binds to the central hydrophobic cavity of TWJ-DNA. Moreover, it could selectively bind to TWJ-DNA over duplex and quadruplex DNA. Furthermore, 2 possesses the capability of serving as the TWJ-DNA probe as its trap-II excimer emission is turned on by TWJ-DNA.