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Octahedral [Pd6L8]12+ metallosupramolecular cages: synthesis, structures and guest-encapsulation studies

Citation

Kim, TY and Digal, L and Gardiner, MG and Lucas, NT and Crowley, JD, Octahedral [Pd6L8]12+ metallosupramolecular cages: synthesis, structures and guest-encapsulation studies, Chemistry: A European Journal, 23, (60) pp. 15089-15097. ISSN 0947-6539 (2017) [Refereed Article]

Copyright Statement

Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: doi:10.1002/chem.201702518

Abstract

Four planar tripyridyl ligands (Ltripy), 1,3,5-tris(pyridin-3-ylethynyl)benzene 1 a, 1,3,5-tris[4-(3-pyridyl)phenyl]benzene 2 a, and the hexyloxy chain functionalized derivatives 1,3,5-tris[(3-hexyloxy-5-pyridyl)ethynyl]benzene 1 b, and 1,3,5-tris[4-(3-hexyloxy-5-pyridyl)phenyl]benzene 2 b, were synthesized and used to generate a family of [Pd6(Ltripy)8](BF4)12 octahedral cages (Ltripy=1 a, b or 2 a, b). The ligands and cages were characterized using a combination of 1H, 13C, and DOSY nuclear magnetic resonance (NMR) spectroscopy, high resolution electrospray mass spectrometry (HR-ESI-MS), infrared (IR) spectroscopy, elemental analysis, and in three cases, X-ray crystallography. The molecular recognition properties of the cages with neutral and anionic guests were examined, in dimethyl sulfoxide (DMSO), using NMR spectroscopy, mass spectrometry and molecular modeling. No binding was observed with simple aliphatic and aromatic guest molecules. However, anionic sulfonates were found to interact with the octahedral cages and the binding interaction was size selective. The smaller [Pd6(1 a, b)8]12+ cages were able to interact with three p-toluenesulfonate guest molecules while the larger [Pd6(2 a, b)8]12+ systems could host four of the anionic guest molecules. To probe the importance of the hydrophobic effect, a mixed water–DMSO (1:1) solvent system was used to reexamine the binding of the neutral organic guests adamantane, anthracene, pyrene and 1,8-naphthalimide within the cages. In this solvent system all the guests except adamantane were observed to bind within the cavities of the cages. NMR spectroscopy and molecular modeling indicated that the cages bind multiple copies of the individual guests (between 3–6 guest molecules per cage).

Item Details

Item Type:Refereed Article
Keywords:cage compounds, host-guest chemistry, metallosupramolecular architectures
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:122790
Year Published:2017
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2017-11-29
Last Modified:2018-03-27
Downloads:0

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