Metal Ion-Induced Formation of Metallogels by Visible-Light-Responsive Phenylalanine-Functionalized Arylazopyrazole Ligands

Abstract

A visible-light-responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand was designed and synthesized, and it was found to form metallogels with reversible photo-responsive properties in mixed methanol/water (MeOH/H2O) solvents. The gelation behavior of the 4-MeS-AAP-NF ligand in the presence of different divalent metal ions in mixed methanol/water (MeOH/H2O) solvents at pH~11.60 was studied. It was found that the 4-MeS-AAP-NF ligand alone could not self-assemble to form any gels. However, in the presence of divalent metal ions, it readily formed the assembled metallogels in an alkaline aqueous/methanol solution with various morphologies. The results suggest that the gelation process was triggered by divalent metal ions. The presence of the AAP moiety in the gel matrix rendered the metallogel assemblies photo-responsive, and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow, reversible visible-light-induced gel-to-sol phase transition under blue (λ = 405 nm) and then sol-to-gel transition by green light (λ = 530 nm) irradiation, resulting in the re-formation of the original gel state. The morphology and viscoelastic properties of the yellow–orange opaque metallogels were characterized by scanning electron microscopy (SEM) and rheological measurement, respectively.

Keywords

• photoswitchable ligand
• arylazopyrazole
• metallogels
• trans-to-cis isomerization