Photoisomerization Dynamics in a Densely Packed Optically Transformable Azobenzene Monolayer.

Molecular monolayers that can be reconfigured through the use of external stimuli promise to enable the creation of interfaces with precisely selected dynamically adjustable physical and electronic properties with potential impact ranging from electronics to energy storage. Azobenzene-containing molecular monolayers have multiple stable molecular conformations but face a challenging nanoscale problem associated with understanding the basic mechanisms of reconfiguration. Time-resolved X-ray reflectivity studies show that the reconfiguration of a densely packed rhenium-azobenzene monolayer occurs in a period of many seconds. The degree of reconfiguration from trans to cis forms depends on the integrated UV fluence and has kinetics that are consistent with a mechanism in which the transformation occurs through the nucleation and growth of nanoscale two-dimensional regions of the cis isomer.