Photo-Switchable Surfactants for Responsive Air-Water Interfaces: Azo vs. Arylazopyrazole Amphiphiles

TL;DR

This study compares azobenzene and arylazopyrazole surfactants, revealing that AAP-based surfactants exhibit significantly greater interfacial property changes upon E/Z isomerization, driven by their molecular structure and interactions.

Contribution

It provides detailed interfacial analysis of AAP versus azo surfactants, highlighting the superior responsiveness of AAPs due to their molecular structure.

Findings

AAP surfactants show larger changes in surface excess upon isomerization.

Interfacial molecular order varies significantly for AAPs but not for azo surfactants.

E/Z isomerization induces substantial interfacial property changes in AAPs.

Abstract

Arylazopyrazoles (AAPs) as substitutes for azo derivatives have gained considerable attention due to their superior properties offering E/Z photo-isomerization with high yield. In order to compare and quantify their performance, azobenzene tetraethylammonium (Azo-TB) and arylazopyrazole tetraethylammonium (AAP-TB) bromides were synthesized and characterized in the bulk (water) using NMR spectroscopy. At the air-water interface complementary information from vibrational sum-frequency generation (SFG) spectroscopy and neutron reflectometry (NR) has revealed the effects of E/Z isomerization in great detail. In bulk water the photostationary states of >89% for E/Z switching in both directions were very similar for the surfactants, while their interfacial behavior was substantially different. In particular, the surface excess $\Gamma$ of the surfactants changed drastically between E/Z isomers for AAP-TB (maximum change of $\Gamma$: 2.15 $\mu$mol/m$^2$); for Azo-TB the change was only moderate (maximum change of $\Gamma$: 1.02 $\mu$mol/m$^2$). Analysis of SFG spectra revealed that strong non-resonant contributions that heterodyned the resonant vibrational bands were proportional to $\Gamma$, enabling the aromatic C-H band to be interpreted as an indicator for changes in interfacial molecular order. Close comparison of $\Gamma$ from NR with the SFG amplitude from the aromatic C-H stretch as a function of concentrations and E/Z conformation revealed substantial molecular order changes for AAP-TB. In contrast, only $\Gamma$ and not the molecular order varied for Azo-TB. These differences in interfacial properties are attributed to the molecular structure of the AAP center that enables favorable lateral interactions at the air-water interface, causing closed-packed interfacial layers and substantial changes during E/Z photo-isomerization.