Catenation and encapsulation induce distinct reconstitutions within a dynamic library of mixed-ligand ZnL cages.

Two new ZnL cages composed of diamine subcomponents containing either naphthalene diimide (NDI) or porphyrin moieties are described. Their structural differences allow these cages to exhibit distinct interactions with different chemical stimuli, yielding different supramolecular products. The electron-poor NDI subunits of the first cage were observed to thread through electron-rich aromatic crown-ether macrocycles, forming mechanically-interlocked species up to a [3]catenane, whereas the porphyrin ligands of the second cage interacted favourably with C, causing it to be bound as a guest.

Stacking Interactions Drive Selective Self-Assembly and Self-Sorting of Pyrene-Based M(II)4L6 Architectures.

Subcomponent self-assembly of two isomeric bis(3-aminophenyl)pyrenes, 2-formylpyridine and the metal ions Fe(II), Co(II), and Zn(II) led to the formation of two previously unidentified structure types: a C2-symmetric M(II)4L6 assembly with meridionally coordinated metal centers, and a C3-symmetric self-included M(II)4L6 assembly with facially coordinated metal centers. In both structures the meta linkages within the ligands facilitate π-stacking between the pyrene panels of the ligands. A C2h-symmetric M(II)2L2 box was also obtained, which was observed to selectively bind electron-deficient aromatic guests between two parallel pyrene subunits.

Disulfide exchange: exposing supramolecular reactivity through dynamic covalent chemistry.

A Tutorial Review of the subtle supramolecular interactions influencing the outcomes of equilibrating systems, focusing on the dynamic covalent chemistry (DCC) of disulfide exchange reactions, is presented. We discuss the topics of cation-π interactions (2.1), hydrophobic effects (2.

Generation of a dynamic system of three-dimensional tetrahedral polycatenanes.

: A dynamic combinatorial library of polycatenated tetrahedra was prepared by complexation between a dynamic FeL tetrahedral cage, constructed from ligands containing an electron‐deficient naphthalenediimide core, and an electron‐rich aromatic crown ether, 1,5‐dinaphtho[38]crown‐10. The highest order species in the library is the tetrahedral [7]catenane.[Image: see text]

Metal-organic container molecules through subcomponent self-assembly.

A variety of different three-dimensional metal-organic container molecules have recently been prepared using subcomponent self-assembly, which relies upon metal template effects to generate complex structures from simple molecular precursors and metal salts. Many of these structures have well defined internal pockets, allowing guest species to be bound and the chemical reactivity of these guests to be modified. Such host molecules have potential applications ranging from the protection of sensitive chemical species to the separation and purification of substrates as diverse as gases, gold compounds, and fullerenes.