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.

Helicene-based π-conjugated macrocycles: their synthesis, properties, chirality and self-assembly into molecular stripes on a graphite surface.

Fully aromatic helicenes are attractive building blocks for the construction of inherently chiral π-conjugated macrocyclic nanocarbons. These hitherto rare molecular architectures are envisaged to exhibit remarkable (chir)optical properties, self-assembly, charge/spin transport, induced ring current or a fascinating Möbius topology. Here the synthesis of helically chiral macrocycles that combine angular dibenzo[5]helicene units as corners and linear trans-stilbene-4,4'-diyl linkers as edges is reported. By subjecting a racemic or enantiopure divinyl derivative of dibenzo[5]helicene to olefin metathesis, which was catalysed by a 2nd generation Piers catalyst under kinetic control, a π-conjugated helicene cyclic trimer (33%) and a tetramer (22%) were obtained, which were separated by GPC. Combining racemic/asymmetric synthesis with the resolution of enantiomers/diastereomers by SFC/HPLC on a chiral column, both homochiral (+)-(M,M,M)/(-)-(P,P,P) and heterochiral (+)-(M,M,P)/(-)-(M,P,P) stereoisomers of the helicene cyclic trimer could be obtained in an enantio- and diastereomerically enriched form. The complete energy profile of their interconversion was compiled on the basis of kinetic measurements and numerical solution of the proposed kinetic model. In equilibrium, the heterochiral diastereomer predominates over the homochiral one (ca. 75 : 25 at 76 °C). π-Conjugation along a large, twisted circuit in the helicene cyclic trimer is rather disrupted, stabilising this formally antiaromatic molecule. Using an optimised PeakForce mode of ambient AFM, the self-assembly of otherwise highly mobile stereoisomers of the helicene cyclic trimer on the HOPG surface could be studied. Irrespective of the stereochemistry, strong preferences for the edge-to-edge interaction of these macrocycles were found to form very long parallel 1D molecular stripes in ordered 2D nanocrystals, a result also supported by molecular dynamics simulations. Six trityl groups, initially introduced to the macrocycle to enhance solubility, serve as a key "molecular Velcro" system in the self-assembly of macrocycles to maximise their mutual van der Waals interactions.

Gram-Scale Synthesis of the 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes.

A gram-scale synthesis of a series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n=7-9) has been accomplished as well as the first synthesis of the next higher homologue 1,1,10,10-tetramethyl[10](2,11)teropyrenophane. The scale-up of the original small-scale synthesis required the development of several heavily modified synthetic methods, including a chlorination/Friedel-Crafts alkylation protocol and an iodination/Wurtz coupling protocol, which were performed on 25-30 g and 30-60 g scales, respectively. Two separate sets of conditions for the key teropyrene-forming cyclodehydrogenation reaction at the end of the synthetic pathway were developed, an acid-promoted one for the two less strained congeners and an acid-free method for the two more strained homologues.

Synthesis of Racemic, Diastereopure, and Enantiopure Carba- or Oxa[5]-, [6]-, [7]-, and -[19]helicene (Di)thiol Derivatives.

A series of carba- or oxa[5]-, [6]-, [7]-, and -[19]helicene (di)thiols was prepared. The Miyazaki-Newman-Kwart rearrangement of (dimethylcarbamothioyl)oxy (oxa)helicenes in a flow reactor or nucleophilic substitution of dichloro (oxa)helicenes with alkanethiolates were used in the sulfanylation step. Despite the high temperatures employed in this key step, no conformational scrambling was observed during the asymmetric synthesis of the diastereo- and enantiopure oxahelicenes. Single-molecule conductivity of the longest oxa[19]helicene dithiol derivative was studied by the scanning tunneling microscopy break-junction method.

Gram-Scale Synthesis and Highly Regioselective Bromination of 1,1,9,9-Tetramethyl[9](2,11)teropyrenophane.

An improved synthetic pathway to the nanobelt-like 1,1,9,9-tetramethyl[9](2,11)teropyrenophane has been developed, and enables the synthesis of gram quantities of material. Key innovations are the development of a sequential chlorination/Friedel-Crafts alkylation reaction, a sequential iodination/Wurtz coupling reaction, and a room-temperature teropyrene-forming reaction. The teropyrenophane was found to form a very stable radical cation and undergo a completely regioselective fourfold bromination reaction.