The effect of carboxylate position on the structure of a metal organic framework derived from cyclotriveratrylene

Abstract

Two cyclotriveratrylene-based ligands H 3 L 1 and H 3 L 2 have been synthesised using microwave heating and used in the formation of 1 [Zn 2 (L 1)(DMA) 2 (CH 3 COO)] and 2 [Zn 6 (L 2) 4 (DMA) 6 (H 2 O) 5 ] (DMA = N, N-dimethylacetamide). 1 displays an unusual trigonal paddlewheel node geometry, while Zn(II) paddlewheels are observed in 2. However, the stacking of CTV molecules in 1 is replaced by an uncommon molecular capsule structure in 2.

Synthesis of Cyclotriveratrylene-Sucrose-Based Capsules

“…The CTV-based molecular hosts gained much attention in recent decades, due to their selective complexing properties toward neutral or charged guests (metals, fullerenes, xenone, and small organic compounds such as epoxides, halogenomethanes, ammonium salts, carbohydrates, neurotransmitters, , or zwitterions). The CTV macrocycles find an application as materials for dendrimers, gelators, or nanostructures . Many of complexation experiments have been studied in organic media, while most of recognition phenomena in nature takes place in water .…”

Two-Dimensional Nanosheets from Redox-Active Superatoms

“…Unusual trinuclear zinc nodes have been reported previously. 44,45 Each zinc atom in Trig 3D exhibits a different coordination environment. Zn 1 and Zn 2 display distorted tetrahedral geometry and together form a three-bladed trigonal paddlewheel with three bridging μ 2 -carboxylates.…”

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

“…9a and b. 24 In this case the capsules are linked through a Zn 2 (carboxylate) 4 dimer with the well-known paddle-wheel structural motif. The capsules of the as-synthesised material contain free and coordinated DMA molecules and there are linked pores throughout the lattice, Fig.…”

“…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.…”

“…The material does not contain significant pores or channels. The complexes [M 2 (OAc)(L20)(DMF) 2 ] where M = Zn or Co reported by Easun and Schröder et al,24 feature 2D coordination polymers with carboxylate-bridged metal-dimers linked by the carboxylate-decorated CTV-type ligand L20 3− into a hexagonal network of decorated 6 3 topology (hcb). Each network contains both ligand enantiomers and the orientation of the ligand bowl (up or down) alternates.…”