Coordination Polymer Chains of Dimeric Pyrogallol[4]arene Capsules

Abstract

Copper seamed dimeric metal-organic pyrogallol[4]arene capsules have been synthesized and engineered into coordination polymer chains, either by direct coordination or with additional bridging ligands. The formation of this copper capsule also demonstrates selective formation of either hexameric or dimeric metal-organic capsules.

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies

“…4 We have previously reported a 2D network of linked metallo-cryptophanes in the complex [Ag 3 (NCMe) 3 (L) 2 Cl] 2+ where L = tris{4-(3-pyridyl)phenylester}cyclotriguaiacylene. 14 In that case the Ag 3 L 2 metallo-cryptophanes were linked through Ag- μ 3 -Cl-Ag bridges, and there were no significant channels through the structure due to the manner of packing between the 2D networks.…”

“…3 Other well-known classes of molecular hosts including calixarenes and related cone-conformation hosts, and cucurbiturils have also been reported to form coordination polymers, often when suitably functionalised with metal-binding groups. 4–6 Cyclotriveratrylene (CTV) is a bowl-shaped molecular host with a tribenzo[ a , d , g ]cyclononatriene core. CTV forms chain and 2D coordination polymers, most commonly with group 1 metal cations.…”

Oxidation State Distributions Provide Insight into Parameters Directing the Assembly of Metal–Organic Nanocapsules

“…[15][16][17][18][19][20][21][22][23][24][25][26][27] In recent times our research has focused on the metal-directed assembly of C-alkylpyrogallol [4]arenes (PgCn, where n is the number of carbon atoms in the pendant alkyl chains). 15,[28][29][30][31][32][33][34][35][36][37] PgCns are bowl-shaped polyphenols and, upon deprotonation, their upper-rim phenolic groups may coordinate to appropriate metal ions, leading to the formation of metal-organic nanocapsules (MONCs). 15,[28][29][30][31][33][34][35][36][37][38] MONCs are primarily self-assembled into two different structural forms, hexamers and dimers.…”

“…15,[28][29][30][31][32][33][34][35][36][37] PgCns are bowl-shaped polyphenols and, upon deprotonation, their upper-rim phenolic groups may coordinate to appropriate metal ions, leading to the formation of metal-organic nanocapsules (MONCs). 15,[28][29][30][31][33][34][35][36][37][38] MONCs are primarily self-assembled into two different structural forms, hexamers and dimers. In this notation, hexamers contain 6 PgCns and 24 metal ions in the general metal-organic cage structure, whilst dimers have 2 and 8 equivalents respectively.…”

Functional diversity in templated solid state reactions

“…The macromolecules Calkylpyrogallol [4]arenes (PgCs) have shown great promise and versatility via their supramolecular interactions both through hydrogen bonding and metal coordinations with copper and zinc. 7 Metallo-PgC capsules have demonstrated functionality as carries for a variety of guest molecules. Through his studies, Atwood has discerned routes for the direct synthesis and assembly of Cu(II) pyrogallol [4]arenes capsules in both the dimeric and hexameric forms ( Figure 3a), resulting in discrete hollow channels that can facilitate transport.…”