Self-Healing Heterometallic Supramolecular Polymers Constructed by Hierarchical Assembly of Triply Orthogonal Interactions with Tunable Photophysical Properties

J Am Chem Soc. 2019 Nov 6;141(44):17909-17917. doi: 10.1021/jacs.9b09671. Epub 2019 Oct 28.

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 does not 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 red-shifts 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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Coordination Complexes / chemistry
  • Crown Ethers / chemistry
  • Light
  • Macromolecular Substances / chemistry*
  • Macromolecular Substances / radiation effects
  • Platinum / chemistry
  • Polymers / chemistry*
  • Polymers / radiation effects
  • Pyridines / chemistry
  • Zinc / chemistry

Substances

  • Coordination Complexes
  • Crown Ethers
  • Macromolecular Substances
  • Polymers
  • Pyridines
  • Platinum
  • Zinc