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Solvent‐Dependent Self‐Assembly Behaviour and Speciation Control of Pd 6 L 8 Metallo‐supramolecular Cages
Author(s) -
Henkelis James J.,
Fisher Julie,
Warriner Stuart L.,
Hardie Michaele J.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304437
Subject(s) - homoleptic , tris , supramolecular chemistry , chemistry , ligand (biochemistry) , stoichiometry , solvent , crystallography , enantiomer , self assembly , solvophobic , stereochemistry , crystal structure , metal , organic chemistry , biochemistry , receptor
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 [Pd 6 L 8 ] 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 MeNO 2 . 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 ( L1 a ). The stoichiometry of reactant mixtures and chemical triggers can be used to control formation of mixtures of homoleptic or heteroleptic [Pd 6 L 8 ] 12+ metallo‐cages where L= L1 and L1 a .