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Exploring the reversible host–guest chemistry of a crystalline octanuclear Ag(I) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand

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Abstract

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.

Graphical abstract: Exploring the reversible host–guest chemistry of a crystalline octanuclear Ag(i) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand

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Publication details

The article was received on 19 Nov 2018, accepted on 21 Nov 2018 and first published on 22 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT04583F
Citation: Dalton Trans., 2018, Advance Article
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    Exploring the reversible host–guest chemistry of a crystalline octanuclear Ag(I) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand

    H. L. Dalton, A. D. Lynes, B. Twamley, K. Byrne, W. Schmitt, C. S. Hawes and T. Gunnlaugsson, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT04583F

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