Solvent‐Dependent Self‐Assembly Behaviour and Speciation Control of Pd₆L₈ Metallo‐supramolecular Cages

Abstract

Abstract:The C 3 -symmetric chiral propylated host-type ligands ()-tris(isonicotinoyl)-tris(propyl)-cyclotricatechylene L1 and ()-tris(4-pyridyl-4-benzoxy)-tris(propyl)-cyclotricatechylene L2

Lanthanide coordination polymers with pyridyl-N-oxide or carboxylate functionalised host ligands

“…[47][48][49][50] The previously unreported ligand (±)-tris(2-quinolylmethyl)-tris(propoxy)-cyclotricatechylene (L2p) was prepared through reaction of propylated-cyclotriguaiacylene (p-CTG) 46 with 2-chloromethylquinoline in basic acetonitrile (MeCN), using an adapted version of a previously reported procedure, and isolated as a racemic mixture in high yields. 47 Ligands L1m, L1p, L2m and L2p were employed as racemic mixtures for all coordination studies and their molecular structures can be seen in Scheme 1.…”

“…Such aggregation was also evident in the previously reported crystal structure of ligand L1p, whereby six individual ligands were observed to pack to create a highly hydrophobic pocket that is filled with six, inwardly-orientated propyl chains, Figure 1a. 46 The stoichiometric reaction of propylated ligand L1p and…”

“…Propylated-cyclotriguaiacylene (p-CTG) was prepared according to literature methods from propylcyclotriveratrylene (p-CTV). 46,58 Ligands L1m, L1p and L2m were prepared according to known literature procedures. 46,47,49 NMR spectra were recorded by automated procedures on a Bruker DPX 500 or 300 MHz NMR spectrometer.…”

“…However, the chemistry of mixed ligand systems is generally limited to the solution-phase, and we have recently demonstrated how the formation and manipulation of homo-and heteroleptic [Pd 6 L 8 ] 12+ octahedral cages can be controlled with high fidelity. 46 These represent examples in which both ligands are suitably pre-designed to undergo metalmediated self-assembly to afford structurally analogous complexes.…”

Self-assembled Cages and Capsules Using Cyclotriveratrylene-type Scaffolds

“…4446 A Pt(II) coordination cage, [Pt 6 (L3) 8 ] 12+ was also observed with the propylated («)-tris(isonicotinoyl)tris(propyl)cyclotricatechylene L3 but this does not form in quantitative yields, unlike the more labile Pd(II) cages. 46 The crystal structure of [Pd 6 (L4) 8 ]…”