Henkelis, JJ, Fisher, J, Warriner, SL et al. (1 more author) (2014) Solvent-dependent self-assembly behaviour and speciation control of Pd 6L8 metallo-supramolecular cages. Chemistry A European Journal, 20 (14). 4117 - 4125. ISSN 0947-6539
Abstract
The C3-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 PdII into [Pd6L8] 12+ metallo-cages that resemble a stella octangula. The self-assembly of the [Pd6(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. All sorted: Stella octangular [Pd6L8]12+ metallo-cages with chiral propylated cyclotriveratrylene-type ligands exhibit homochiral self-sorting in MeCN or MeNO2 but not in DMSO. Furthermore, differences in the favourability of the metallo-cage with propylated or methylated ligands can be used to control speciation in solution from heteroleptic to predominantly single homoleptic to dual homoleptic metallo-cages.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | This is the peer reviewed version of the following article:Henkelis, JJ, Fisher, J, Warriner, SL and Hardie, MJ (2014) Solvent-dependent self-assembly behaviour and speciation control of Pd 6L8 metallo-supramolecular cages. Chemistry A European Journal, 20 (14). 4117 - 4125 , which has been published in final form athttp://dx.doi.org/10.1002/chem.201304437 This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving. |
Keywords: | Coordination cage; ligand exchange; self-assembly; self-sorting; supramolecular chemistry |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 27 Nov 2014 14:28 |
Last Modified: | 20 Apr 2015 13:18 |
Published Version: | http://dx.doi.org/10.1002/chem.201304437 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/chem.201304437 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:81576 |