Solvent‐Dependent Self‐Assembly Behaviour and Speciation Control of Pd6L8 Metallo‐supramolecular Cages. Issue 14 (3rd March 2014)

• Record Type: Journal Article
• Authors: Henkelis, James J.; Fisher, Julie; Warriner, Stuart L.; Hardie, Michaele J.
• Is Part Of: Chemistry. Volume 20:Issue 14(2014)
• Page Start: 4117
• Page End: 4125
• Publication Date: 2014-03-03
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201304437
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The <italic>C</italic>₃‐symmetric chiral propylated host‐type ligands (±)‐<italic>tris</italic>(isonicotinoyl)‐<italic>tris</italic>(propyl)‐cyclotricatechylene (<bold>L1</bold>) and (±)‐<italic>tris</italic>(4‐pyridyl‐4‐benzoxy)‐<italic>tris</italic>(propyl)‐cyclotricatechylene (<bold>L2</bold>) self‐assemble with Pd^II into [Pd₆L₈]¹²⁺ metallo‐cages that resemble a stella octangula. The self‐assembly of the [Pd₆(<bold>L1</bold>)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 [Pd₆(<bold>L1</bold>)₈]¹²⁺ cage is observed to be less favourable in the presence of additional ligand, than is its counterpart, where L=(±)‐<italic>tris</italic>(isonicotinoyl)cyclotriguaiacylene (<bold>L1 a</bold>). 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=<bold>L1</bold> and <bold>L1 a</bold>.</p> </abstract>