The realization of controllable and well-organized self-assembly within multicomponent supramolecular systems (MSSs) is still a great challenge. Herein, we present the construction of multicomponent supramolecular systems with high-level complexity through the combination of orthogonal self-assembly and the self-sorting approach. Driven by the orthogonality of metal–ligand coordination and host–guest interactions in the orthogonal self-assembly as well as directed by multiple molecular codes in the self-sorting process, five types of simple components (up to eighteen precursors) were successfully self-assembled into two novel tris[2]pseudorotaxanes in one pot through a highly selective manner, which were well-characterized by one-dimensional (1-D) and two-dimensional (2-D) multinuclear NMR as well as ESI-TOF-MS.

A pillar[5]arene decaamine has been synthesized and revealed to encapsulate linear diacids in neutral, alkaline, and acidic conditions, driven by the hydrophobic and electrostatic interactions, to give rise to pseudo[2]rotaxanes. Ion pair-bonded stoppers can further lock the diacids to generate stable water soluble [2]rotaxanes.

In the present study, we focus on the interactions between poly(propylene imine) (PPI) dendrimer and 18 of the 20 common amino acids by several NMR techniques, including NMR titrations and NOESY analysis. Surface ionic interactions and interior encapsulations were observed, and the binding behavior of amino acids with PPI dendrimer depends much on the side-chain properties of the amino acid, such as charge and hydrophobic/hydrophilic properties. The 1H NMR titration results show that the formation of PPI dendrimer–amino acid complexes are driven mainly by ionic interactions for all the amino acids except tryptophan, which is involved in strong hydrophobic interactions with the interior pockets of PPI. The hydrophobic encapsulation of tryptophan in PPI pockets is confirmed by NOESY analysis. Amino acids with negatively charged residues much more easily saturate the surface charges on PPI than amino acids with uncharged residues, whereas amino acids with positively charged residues are the most difficult to bind with the surface amine groups on the PPI dendrimer. A simultaneous occurrence of interior encapsulation (hydrophobic, hydrogen bond, or ionic interactions) and surface binding (ionic interactions) was observed for tryptophan, phenylalanine, arginine, lysine, histidine, cysteine, and asparagine, and a preferential surface ionic binding on the PPI surface rather than encapsulations in the interior was obtained for the other amino acids.

A pillar[5]arene decaamine has been synthesized and revealed to encapsulate linear diacids in neutral, alkaline, and acidic conditions, driven by the hydrophobic and electrostatic interactions, to give rise to pseudo[2]rotaxanes. Ion pair-bonded stoppers can further lock the diacids to generate stable water soluble [2]rotaxanes.

The realization of controllable and well-organized self-assembly within multicomponent supramolecular systems (MSSs) is still a great challenge. Herein, we present the construction of multicomponent supramolecular systems with high-level complexity through the combination of orthogonal self-assembly and the self-sorting approach. Driven by the orthogonality of metal–ligand coordination and host–guest interactions in the orthogonal self-assembly as well as directed by multiple molecular codes in the self-sorting process, five types of simple components (up to eighteen precursors) were successfully self-assembled into two novel tris[2]pseudorotaxanes in one pot through a highly selective manner, which were well-characterized by one-dimensional (1-D) and two-dimensional (2-D) multinuclear NMR as well as ESI-TOF-MS.