2D networks of metallo-capsules and other coordination polymers from a hexapodal ligand

Abstract

2D M3L2 coordination polymers (M = Re(i), Cu(ii), Co(ii), Ni(ii)) feature metal-linked M6L2-cages, and the Re(i) material absorbs iodine.

Coordination polymers with embedded recognition sites: lessons from cyclotriveratrylene-type ligands

“…In this example the hexapodal L2 acts as the 6-connecting centre and the Ag(I) as a trigonal centre. 21 It does not have the tubular structure shown for the previously discussed kgd material [Zn(L17) 2 ] 2+ , 17 Fig. 13b, but rather the 2D network has a wavelike aspect.…”

“…Intra-cavity guest binding occurs where a molecular guest occupies the cavity of the host CTV-ligand, most commonly with a hydrophobic part of the guest molecule directed into the hydrophobic cavity of the host. Examples include (L2)•(MeNO 2 ), 21 1a. A similar capsule-like motif is seen for L1 crystallised from CH 2 -Cl 2 /hexane however the presence of an intra-cavity guest could not be established crystallographically.…”

“…Thus far, reports of applications of these materials are limited. Guest exchange or guest uptake has been established in some cases, and includes inclusion of small solvent molecules, 26 iodine, 21 and larger fullerene guests. 20 with complete exchange of solvent to an isomorphic structure.…”

“…Pillararenes, crown ethers, cucurbiturils and cyclodextrins have also been employed. Our own work, [9][10][11][12][13][14][15][16][17][18][19][20][21] alongside that of other research groups, [22][23][24][25][26] has investigated the use of functionalised cyclotriveratrylenes (CTVs) as bridging ligands for coordination polymers. Cyclotriveratrylene (CTV) is a bowl-shaped molecular host with a tribenzo [a,d,g] cyclononatriene core.…”

Controlled Access to C1‐Symmetrical Cyclotriveratrylenes (CTVs) by Using a Sequential Barluenga Boronic Coupling (BBC) Approach

“…C 3 -Symmetrical CTVs have found a wide variety of uses as ion or organic molecule sensors [2,3] building blocks for liquid crystals [3] or purification devices. [4][5][6] CTVs are also known to be precursors in supramolecular assemblies such as capsules, [7][8][9] cryptophanes [10][11][12][13][14][15][16][17][18] and hemicryptophanes. [19][20][21][22][23][24][25][26] To date, most of these applications are based on the use of C 3symmetrical CTVs and, for decades, C 3 -symmetrical CTVs have been synthesized from the corresponding substituted benzylic alcohols through cyclotrimerization using acidic conditions such as perchloric acid in methanol, [27] sulfuric acid in acetic acid, [10] formic acid [28] or scandium triflate.…”