Selective Encapsulation and Sequential Release of Guests Within a Self‐Sorting Mixture of Three Tetrahedral Cages

Abstract

A mixture of two triamines, one diamine, 2-formylpyridine and a Zn(II) salt was found to self-sort, cleanly producing a mixture of three different tetrahedral cages. Each cage bound one of three guests selectively. These guests could be released in a specific sequence following the addition of 4-methoxyaniline, which reacted with the cages, opening each in turn and releasing its guest. The system here described thus behaved in an organized way in three distinct contexts: cage formation, guest encapsulation, and guest release. Such behavior could be used in the context of a more complex system, where released guests serve as signals to other chemical actors.

Peripheral Templation Generates an MII6L4 Guest‐Binding Capsule

“…These volumes are approximately ten times larger than those of the M II 4 L 4 tetrahedra formed from the same triamines using 2-formylpyridine. [17] We reasoned that, given the tetrahedrally arranged apertures of the hosts, we could employ the voids of 1-3 to bind tetrahedral guests. Three classes of tetrahedral prospective guests were investigated: neutral molecules, smaller anions, and larger anions incorporating aromatic units.…”

Heterometallic transition metal clusters and cluster-supported coordination polymers derived from Tp- and Tp*-based Mo(W) sulfido precursors

“…The cage compounds, extensively studied in the last few decades by Fujita, Raymond, Nitschke and others [115][116][117][118][119][120][121][122][123][124][125][126], are a fascinating class of discrete molecular entities capable of altering molecular behavior within the confined space, and termed as 'molecular flasks' by Fujita [127]. The geometrical advantage of Tp and Tp* along with MS 3 Cu 3 (M = Mo, W) in favoring tetrahedral cages may allow us to approach other cage compounds with relative ease.…”

Ligand Constraints and Synthesis of Metal–Organic Polyhedra

“…The D 4 isomer of Cu 8 L 4 ÁBF 4 is capable of binding the complex anion Cu(Au(CN) 2 ) 2 À and copper ion bridges the two NC-Au-CN À and could be substituted by AgI to afford Ag(Au (CN) 2 ) 2 À adduct of Cu 8 L 4 -D 4 ÁBF 4 . Using the same strategy, M 4 L 4 (1, 2) and M 4 L 6 (3) discrete metal-organic capsules were synthesised by tris(4-aminophenol)methanol (A), 1,3,5-tris(4aminophenyl)amine (B), 4,4 0 -diaminobiphenyl (C), respectively, in combination with 2-formyl pyridine and Zn II salts [136] as shown in Fig. 27.…”