A Reduced-Symmetry Heterobimetallic [PdPtL4]4+ Cage: Assembly,Guest Binding,and Stimulus-Induced Switching |
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| Authors: | Lynn S. Lisboa Dr. James A. Findlay Prof. L. James Wright Prof. Christian G. Hartinger Prof. James D. Crowley |
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| Affiliation: | 1. Department of Chemistry, University of Otago, PO Box 56, Dunedin, 9054 New Zealand;2. School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland, 1142 New Zealand |
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| Abstract: | A strategy is presented that enables the quantitative assembly of a heterobimetallic [PdPtL4]4+ cage. The presence of two different metal ions (PdII and PtII) with differing labilities enables the cage to be opened and closed selectively at one end upon treatment with suitable stimuli. Combining an inert PtII tetrapyridylaldehyde complex with a suitably substituted pyridylamine and PdII ions led to the assembly of the cage. 1H and DOSY NMR spectroscopy and ESI mass spectrometry data were consistent with the quantitative formation of the cage, and the heterobimetallic structure was confirmed using single-crystal X-ray crystallography. The structure of the host–guest adduct with a 2,6-diaminoanthraquinone guest molecule was determined. Addition of N,N′-dimethylaminopyridine (DMAP) resulted in the formation of the open-cage [PtL4]2+ compound and [Pd(DMAP)4]2+ complex. This process could then be reversed, with the reformation of the cage, upon addition of p-toluenesulfonic acid (TsOH). |
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| Keywords: | cages heterometallic complexes host–guest systems metallosupramolecular architectures stimuli-responsiveness |
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