Supramolecular Control of Azobenzene Switching on Nanoparticles

Zonglin Chu, Yanxiao Han, Tong Bian, Soumen De, Petr Král, Rafal Klajn

Research output: Contribution to journalArticle

Abstract

The reversible photoisomerization of azobenzene has been utilized to construct a plethora of systems in which optical, electronic, catalytic, and other properties can be controlled by light. However, owing to azobenzene's hydrophobic nature, most of these examples have been realized only in organic solvents, and systems operating in water are relatively scarce. Here, we show that by coadsorbing the inherently hydrophobic azobenzenes with water-solubilizing ligands on the same nanoparticulate platforms, it is possible to render them essentially water-soluble. To this end, we developed a modified nanoparticle functionalization procedure allowing us to precisely fine-tune the amount of azobenzene on the functionalized nanoparticles. Molecular dynamics simulations helped us to identify two distinct supramolecular architectures (depending on the length of the background ligand) on these nanoparticles, which can explain their excellent aqueous solubilities. Azobenzenes adsorbed on these water-soluble nanoparticles exhibit highly reversible photoisomerization upon exposure to UV and visible light. Importantly, the mixed-monolayer approach allowed us to systematically investigate how the background ligand affects the switching properties of azobenzene. We found that the nature of the background ligand has a profound effect on the kinetics of azobenzene switching. For example, a hydroxy-terminated background ligand is capable of accelerating the back-isomerization reaction by more than 6000-fold. These results pave the way toward the development of novel light-responsive nanomaterials operating in aqueous media and, in the long run, in biological environments.

Original languageEnglish
Pages (from-to)1949-1960
Number of pages12
JournalJournal of the American Chemical Society
Volume141
Issue number5
DOIs
Publication statusPublished - Feb 6 2019

Fingerprint

Azobenzene
Nanoparticles
Ligands
Photoisomerization
Water
Light
Nanostructures
Molecular Dynamics Simulation
Ultraviolet Rays
Isomerization
azobenzene
Nanostructured materials
Solubility
Organic solvents
Molecular dynamics
Monolayers
Kinetics
Computer simulation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Supramolecular Control of Azobenzene Switching on Nanoparticles. / Chu, Zonglin; Han, Yanxiao; Bian, Tong; De, Soumen; Král, Petr; Klajn, Rafal.

In: Journal of the American Chemical Society, Vol. 141, No. 5, 06.02.2019, p. 1949-1960.

Research output: Contribution to journalArticle

Chu, Zonglin ; Han, Yanxiao ; Bian, Tong ; De, Soumen ; Král, Petr ; Klajn, Rafal. / Supramolecular Control of Azobenzene Switching on Nanoparticles. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 5. pp. 1949-1960.
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