The controlled attachment of chromophores to metal or semiconducting surfaces is a prerequisite for the construction of photonic devices and artificial surface-based light-harvesting systems. We present an approach to mount porphyrins in ordered monolayers on Au(111) by self-assembly and verify it, employing STM, absorption spectroscopy, and quantum chemical calculations. The usual adsorption geometry of planar chromophores, flat on the surface or densely packed edge-on, is prevented by mounting the porphyrins upright on a molecular platform. An ethynyl unit as spacer and pivot joint provides almost free azimuthal rotation of the unsubstituted porphin. However, rotation of the larger triphenylporphyrin unit is sterically restricted: because the diameter of the substituted porphyrin is larger than the distance to its next neighbors, the phenyl substituents of neigboring molecules interact by dispersion force, which leads to an alignment of the azimuthal rotators.

Direct comparative studies of the photoisomerization of azobenzene derivatives in self-assembled adlayers on Au and as free molecules in dichloromethane solution were performed using UV/vis spectroscopy. For all studied systems a highly reversible trans-cis isomerization in the adlayer is observed. Quantitative studies of the absorbance changes and photoisomerization kinetics reveal that in azobenzenes mounted as freestanding vertical groups on the surface via triazatriangulene-based molecular platforms photoswitching is nearly uninhibited by the local environment in the adlayer. The blue-shift of the π-π* transition in adlayers of these molecules is in good agreement with theoretical studies of the effect of excitonic coupling between the molecules. In contrast, in azobenzene-containing thiol self-assembled monolayers the fraction of photoswitching molecules and the photoisomerization kinetics are significantly reduced compared to free molecules in solution.

Triazatriangulenium (TATA) platforms have been used to prepare highly ordered, self-assembled monolayers of free- and vertically standing imines on Au(111) surfaces. Upon irradiation, the imines undergo trans-cis isomerization and a fast thermal reaction (t1/2 =0.58 s at 20 °C) back to the more stable trans form. It is known that the photochemical reaction proceeds through rotation of the C=N bond and the thermochemical reaction through inversion at the N atom. The imine motors, therefore, should be able to induce a net displacement of particles above the surface similar to cilia epithelia in nature.

Glycolipids as constituents of cell membranes play an important role in cell membrane functioning. To enable the structural modification of membranes on demand, embedding of photosensitive glycolipid mimetics was envisioned and novel amphiphilic glycolipid mimetics comprising a photoswitchable azobenzene unit were synthesized. In this study, the photochromic properties of these glycolipid mimetics were analyzed by means of UV/Vis spectroscopy and reversible photoswitching. The glycolipids were based on a racemic glycerolipid derivative to be comparable in DPPC (dipalmitoylphosphatidylcholine) phospholipid membrane monolayers. Carbohydrate head groups were altered between a β‐glucoside and a β‐lactosyl unit, as well as acyl chain lengths between C12 and C16, resulting in altered photoswitching. Langmuir isotherms showed that photoswitching of Langmuir films comprising the synthetic photosensitive glycoamphiphiles was successful.

Rotors and switches are elementary building blocks of molecular machines. To achieve more advanced functions, these units have to be integrated into solid-state devices, which triggered interest in mounting these functional units in well-defined geometries onto surfaces. While vertically oriented switches and rotors have been obtained by various strategies, the design of surface-parallel switches and of altitudinal rotors with an in-plane oriented rotation axis has proven to be more difficult. We here demonstrate a molecular adlayer system with highly defined geometry and laterally oriented functional groups that combines facile photoswitching and rotation. We employ a custom-designed molecule with two platforms and pillars that span an azobenzene unit between them. The molecules form well-ordered monolayers on Au(111) with the azobenzene units parallel to and above the surface. Spectroscopic data and density functional calculations suggest that in the trans configuration, at room temperature, the azo unit is freely rotating. Upon irradiation with UV light, the azo unit switches to the bent cis configuration and rotation stops. Irradiation with 430 nm restores the rotating trans state. Notably, the photochemistry is not quenched by the metal surface. This approach offers a promising strategy to operate molecular machines on metal surfaces with light, which is still a major problem in molecular nanotechnology.