Self-Healing Heterometallic Supramolecular Polymers Constructed by Hierarchical Assembly of Triply Orthogonal Interactions with Tunable Photophysical Properties
- 16 October 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 141 (44), 17909-17917
- https://doi.org/10.1021/jacs.9b09671
Abstract
Here we present a method for the building of new bicyclic heterometallic cross-linked supramolecular polymers by hierarchical unification of three types of orthogonal noncovalent interactions, including platinum(II)-pyridine coordination-driven self-assembly, zinc-terpyridine complex and host–guest interactions. The platinum-pyridine coordination provides the primary driving force to form discrete rhomboidal metallacycles. The assembly doesn’t interfere with the zinc-terpyridine complexes, which link the discrete metallacycles into linear supramolecular polymers, and the conjugation length is extended upon the formation of the zinc-terpyridine complexes, which redshifts the absorption and emission spectra. Finally, host-guest interactions via bis-ammonium salt binding to the benzo-21-crown-7 (B21C7) groups on the platinum acceptors afford the cross-linked supramolecular polymers. By continuous increase of the concentration of the supramolecular polymer to a relatively high level, supramolecular polymer gel is obtained, which exhibits self-healing properties and reversible gel−sol transitions stimulated by various external stimuli, including temperature, K+ and cyclen. Moreover, the photophysical properties of the supramolecular polymers could be effectively tuned by varying the substituents of the precursor ligands.Keywords
Funding Information
- Foundation for the National Institutes of Health (R01-CA215157)
- China Scholarship Council
- National Natural Science Foundation of China (51703046, 21971049, 21574034)
- Natural Science Foundation of Zhejiang Province (LQ18B040001, LY16B040006)
This publication has 53 references indexed in Scilit:
- Facile Catch and Release of Fullerenes Using a Photoresponsive Molecular TubeJournal of the American Chemical Society, 2013
- Highly stretchable and tough hydrogelsNature, 2012
- Switchable Supramolecular Polymers from the Self-Assembly of a Small Monomer with Two Orthogonal Binding InteractionsJournal of the American Chemical Society, 2011
- Emerging applications of stimuli-responsive polymer materialsNature Materials, 2010
- Supramolecular polymersNature, 2008
- Self-healing and thermoreversible rubber from supramolecular assemblyNature, 2008
- Supramolecular Allosteric Cofacial Porphyrin ComplexesJournal of the American Chemical Society, 2006
- Coordination Assemblies from a Pd(II)-Cornered Square ComplexAccounts of Chemical Research, 2005
- Supramolecular gels: Functions and usesChemical Society Reviews, 2005
- Multistimuli, Multiresponsive Metallo-Supramolecular PolymersJournal of the American Chemical Society, 2003