Dalton, HL, Lynes, AD, Twamley, B, Byrne, K, Schmitt, W, Hawes, CS and Gunnlaugsson, T (2018) Exploring the reversible host-guest chemistry of a crystalline octanuclear Ag(I) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand. Dalton Transactions, 47 (48). pp. 17266-17275. ISSN 1477-9226

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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.

Item Type: Article
Additional Information: The final published version of this article is available online at https://pubs.rsc.org/en/Content/ArticleLanding/2018/DT/C8DT04583F#!divAbstract
Uncontrolled Keywords: chemistry
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural Sciences > School of Chemical and Physical Sciences
Depositing User: Symplectic
Date Deposited: 26 Nov 2018 12:48
Last Modified: 22 Nov 2019 05:03
URI: https://eprints.keele.ac.uk/id/eprint/5526

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