Exploring the reversible host–guest chemistry of a crystalline octanuclear Ag(i) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand
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2018Access:
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Dalton, H.L., Lynes, A.D., Twamley, B., Byrne, K., Schmitt, W., Hawes, C.S., Gunnlaugsson, T., Exploring the reversible host-guest chemistry of a crystalline octanuclear Ag(i) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand', Dalton Transactions, 2018, 48Abstract:
Here we report the synthesis of two new 2-(2′-pyrazinyl)pyridine ligands, and explore their coordination chemistry with Cu(II) and Ag(I) ions, leading to the discovery of metallosupramolecular architectures of surprising complexity. Differing only in the substitution pattern of a nitrophenyl substituent attached to the 4-pyridyl position, ligands L1 and L2 both form sulfate-bridged dinuclear complexes on reaction with copper sulfate, without coordination of the nitrogen atom at the pyrazine 4-position. However, on reaction with Ag(I), both ligands adopt bridging coordination modes which lead to dramatically different outcomes. Ligand L2 reacts with AgCF3SO3 to give a densely packed coordination polymer 3 of unusually low symmetry (Z′ = 7), while the structural isomer L1 instead gives an octanuclear macrocycle 4 in the crystalline state. Macrocycle 4, containing crystallographically-defined solvent molecules within its central cavity as well as in the interstitial spaces, readily undergoes solvent exchange in a single-crystal-to-single-crystal transformation. This allows a direct comparison of guest solvent affinity from single component and mixed-component exchange solutions using a combination of X-ray diffraction, NMR and TGA techniques, revealing the fully reversible uptake and exchange preferences of this material.
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Grant Number
Science Foundation Ireland
13/IA/1865
Author's Homepage:
http://people.tcd.ie/gunnlauthttp://people.tcd.ie/schmittw
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Dalton Transactions;48;
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Silver compounds, Hostguest chemistry, ChelationDOI:
http://dx.doi.org/10.1039/C8DT04583FMetadata
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