Regular Arrays of Rod-Shaped Molecular Photoswitches: Synthesis, Preparation, Characterization, and Selective Photoswitching within Mono- and Bilayer Systems.

We assembled photoresponsive mono- and bilayer systems with well-defined properties from rod-shaped molecules equipped with different photoswitches. Using properly chosen chromophores (diarylethene-based switch and unidirectional light-driven molecular motor), we then selectively targeted layers made of the same types of photoswitches using appropriate monochromatic light. UV-vis analysis confirmed smooth and unrestricted photoisomerization. To achieve this, we synthesized a new class of triptycene-based molecular pedestals adept at forming sturdy Langmuir-Blodgett films on a water-air interface. The films were smoothly transferred to gold and quartz surfaces. Repeated deposition afforded bilayer systems: one layer containing diarylethene-based photoswitches and the other a unidirectional light-driven molecular motor. Structural analysis of both mono- and bilayer systems revealed the molecules to be tilted with carboxylic functions pointing to the surface. At least two different polymorphs differing in monolayer thickness and tilt angle (~40° and ~60°) were identified on the gold surface.

Triptycene-Based Molecular Rods for Langmuir-Blodgett Monolayers.

Herein we introduce fully modular synthesis leading to three representative examples of rigid molecular rods that are intended to form sturdy monolayers on various surfaces. These molecules contain two triptycene units that are designed to interlock into a compact "double-decker" structure. Two of the three final products provided suitable crystals for X-ray diffraction (analyzed on synchrotron), allowing deeper insight into packing in the 3-D crystal lattice. The acidity of all three compounds were determined by capillary electrophoresis, and the pKa values ranged between 2.06-2.53. All three rigid rods easily formed Langmuir-Blodgett monolayers (LBMs) on the water-air interfaces, with the area per molecule equal to 55-59 Å2 /molecule, suggesting tight intermolecular packing. The thickness of all three films reached ∼19 Šafter transfer to a gold (111) surface, meaning that individual molecules are tilted maximally 38° from the axis perpendicular to the surface. The structure of one of these films on a gold (111) surface was visualized by AFM. These geometrically unique molecules represent promising platforms with a wide scope of applicability in the supramolecular architecture.

Regular Two-Dimensional Arrays of Surface-Mounted Molecular Switches: Switching Monitored by UV-vis and NMR Spectroscopy.

Using solid-state 15N NMR spectroscopy, the cis/trans isomerization in a two-dimensional (2-D) array of surface-mounted azobenzene-based switches was detected for the first time. In order to achieve this, a new class of rod-shaped molecular switches, suitable for formation of 2-D regular arrays on large facets of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) nanocrystals, was synthesized. A mechanochemical approach was used to prepare corresponding host-guest surface inclusions in a TPP matrix. Comparison of thermal steps in solution and supramolecular surface inclusions revealed that switching of individual molecules is not compromised by the close proximity of neighbors.