Chris Hawes c.s.hawes@keele.ac.uk
Exploring the reversible host-guest chemistry of a crystalline octanuclear Ag(I) metallosupramolecular macrocycle formed from a simple pyrazinylpyridine ligand
Hawes, Chris S.
Authors
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.
Acceptance Date | Nov 21, 2018 |
---|---|
Publication Date | Dec 28, 2018 |
Journal | Dalton Transactions |
Print ISSN | 1477-9226 |
Publisher | Royal Society of Chemistry |
Pages | 17266-17275 |
DOI | https://doi.org/10.1039/C8DT04583F |
Keywords | chemistry |
Publisher URL | https://pubs.rsc.org/en/Content/ArticleLanding/2018/DT/C8DT04583F#!divAbstract |
Files
Manuscript.docx
(8.9 Mb)
Document
Publisher Licence URL
https://creativecommons.org/licenses/by-nc/4.0/
You might also like
Fused aza-heterocyclic ligands: expanding the MOF chemist's toolbox
(2022)
Journal Article
A Reversibly Porous Supramolecular Peptide Framework**
(2022)
Journal Article
Downloadable Citations
About Keele Repository
Administrator e-mail: research.openaccess@keele.ac.uk
This application uses the following open-source libraries:
SheetJS Community Edition
Apache License Version 2.0 (http://www.apache.org/licenses/)
PDF.js
Apache License Version 2.0 (http://www.apache.org/licenses/)
Font Awesome
SIL OFL 1.1 (http://scripts.sil.org/OFL)
MIT License (http://opensource.org/licenses/mit-license.html)
CC BY 3.0 ( http://creativecommons.org/licenses/by/3.0/)
Powered by Worktribe © 2024
Advanced Search