Dynamic Wetting of Photo-Responsive Arylazopyrazole Monolayers is Controlled by the Molecular Kinetics of the Monolayer

Smart surfaces that can change their wetting behavior on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. In order to functionalize aluminum oxide surfaces, we have synthesized arylazopyrazole phosphonic acids (butyl-AAP-C18PA) that represent a new class of photoswitchable molecules for these oxide surfaces. Butyl-AAP-C18PA monolayers were deposited on alpha-Al2O3(0001) and show reversible E/Z photo-switching with UV (Z) and green (E) light that can trigger contact angle changes of up to ~10°. We monitored these changes on the macroscopic level by recording the dynamic contact angle while the monolayer was switched in situ from the E to the Z state. On the molecular level, time-resolved vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the relevant characteristic time scales for E to Z switching and vice versa. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water and that water can stabilize the Z state and, thus, hinder the AAP monolayer to switch into the E state when it is immersed in H2O. Having established the characteristic times for switching on the molecular scale from SFG spectroscopy, we additional measure the dynamic contact angle. Further, we reveal the time scales of the coupled substrate and droplet dynamics which we have extracted individually. For that, we report on a relaxation model, that can be solved analytically and which is verified via comparison with simulations of a Lennard Jones system and a comparison with experimental data. Indeed, our modelling of these coupled relaxation processes allows us to predict the non-trivial variation of the time-dependence of the contact angle when changing the size of the droplet. The observed slowing-down for E to Z switching upon the presence of the droplet is rationalized in terms of specific interactions of water with the exposed AAP moieties.