Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 14, Pages 4117-4125Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201304437
Keywords
coordination cage; ligand exchange; self-assembly; self-sorting; supramolecular chemistry
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Funding
- EPSRC
- Brotherton Trust
- Engineering and Physical Sciences Research Council [EP/C010973/1] Funding Source: researchfish
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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) self-assemble with Pd-II into [Pd6L8](12+) metallo-cages that resemble a stella octangula. The self-assembly of the [Pd-6(L1)(8)](12+) cage is solvent-dependent; broad NMR resonances and a disordered crystal structure indicate no chiral self-sorting of the ligand enantiomers in DMSO solution, but sharp NMR resonances occur in MeCN or MeNO2. The [Pd-6(L1)(8)](12+) cage is observed to be less favourable in the presence of additional ligand, than is its counterpart, where L=(+/-)-tris(isonicotinoyl)cyclotriguaiacylene (L1a). The stoichiometry of reactant mixtures and chemical triggers can be used to control formation of mixtures of homoleptic or heteroleptic [Pd6L8](12+) metallo-cages where L=L1 and L1a.
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