A Scanning Tunneling Microscopy Study of the Photoisomerization of Diazocine.

Azobenzenes are fascinating molecular machines that can reversibly transform between two isomeric forms by an external stimulus. Diazocine, a type of bridged azobenzene, has been shown to possess enhanced photoexcitation properties. Due to the distortion caused by the ethyl bridge in the E-isomer, the Z-form becomes the thermodynamically stable configuration. Despite a comprehensive understanding of its photophysical properties, there is still much to learn about the behavior of diazocine on a metal surface. Here we show the operando photoswitching of diazocine molecules deposited directly on a Au(111) surface using scanning tunneling microscopy. Molecules were shown to aggregate into disordered islands with edge sites being susceptible to photon-induced movement. A few molecules were shown to undergo directional movement under UV irradiation with the motion reversed under blue light exposure. These findings contribute new insight into the activity of single and ensemble molecular systems toward purposefully guided motion.

Light-induced Photoswitching of 4-(Phenylazo)benzoic Acid on Au(111).

Photochromic molecules can undergo a reversible conversion between two isomeric forms upon exposure to external stimuli such as electromagnetic radiation. A significant physical transformation accompanying the photoisomerization process defines them as photoswitches, with potential applications in various molecular electronic devices. As such, a detailed understanding of the photoisomerization process on surfaces and the influence of the local chemical environment on switching efficiency is essential. Herein, we use scanning tunneling microscopy to observe the photoisomerization of 4-(phenylazo)benzoic acid (PABA) assembled on Au(111) in kinetically constrained metastable states guided by pulse deposition. Photoswitching is observed at low molecular density and is absent in tight-packed islands. Furthermore, switching events were noted in PABA molecules coadsorbed in a host octanethiol monolayer, suggesting an influence of the surrounding chemical environment on photoswitching efficiency.

Electronic energy levels of porphyrins are influenced by the local chemical environment.

Self-assembled islands of 5,10,15,20-tetrakis(pentafluoro-phenyl)porphyrin (2HTFPP) on Au(111) contain two bistable molecular species that differ by shifted electronic energy levels. Interactions with the underlying gold herringbone reconstruction and neighboring 2HTFPP molecules cause approximately 60% of molecules to have shifted electronic energy levels. We observed the packing density decrease from 0.64 ± 0.04 molecules per nm2 to 0.38 ± 0.03 molecules per nm2 after annealing to 200 °C. The molecules with shifted electronic energy levels show longer-range hexagonal packing or are adjacent to molecular vacancies, indicating that molecule-molecule and molecule-substrate interactions contribute to the shifted energies. Multilayers of porphyrins do not exhibit the same shifting of electronic energy levels which strongly suggests that molecule-substrate interactions play a critical role in stabilization of two electronic species of 2HTFPP on Au(111).