Abstract: The self-assembly of corrole trimers in solution and at solid–liquid interfaces is a process that depends on dewetting, hydrogen bonding and – interactions between the molecules forming columnar stacks, and lateral interactions between these stacks to generate higher order assemblies.
Abstract: We have investigated in detail the self-assembly of a chiral porphyrin trimer in different solvents and correlated this behavior to the aggregation of the molecule at a solid-liquid interface. In n-hexane and cyclohexane, CD spectroscopy and dynamic and static light scattering studies showed that the porphyrin trimer self-assembles already at micromolar concentrations into long, chiral supramolecular polymers, which precipitate as fibers when the solution is drop-cast onto a mica surface. In contrast, in chloroform, the compound is molecularly dissolved up to concentrations of 0.2 mM and when micromolar solutions are drop-cast onto mica, no precipitation of large assemblies occurs. Instead, at the moment that the chloroform film becomes subject to spinodal dewetting and the porphyrin trimers within this film start to self-assemble, extended patterns of equidistant lines of single molecule thick columnar stacks are formed.
Abstract: Many chemical reactions are catalysed by metal complexes, and insight into their mechanisms is essential for the design of future catalysts. A variety of conventional spectroscopic techniques are available for the study of reaction mechanisms at the ensemble level, and, only recently, fluorescence microscopy techniques have been applied to monitor single chemical reactions carried out on crystal faces and by enzymes. With scanning tunnelling microscopy (STM) it has become possible to obtain, during chemical reactions, spatial information at the atomic level. The majority of these STM studies have been carried out under ultrahigh vacuum, far removed from conditions encountered in laboratory processes. Here we report the single-molecule imaging of oxidation catalysis by monitoring, with STM, individual manganese porphyrin catalysts, in real time, at a liquid-solid interface. It is found that the oxygen atoms from an O2 molecule are bound to adjacent porphyrin catalysts on the surface before their incorporation into an alkene substrate.
Abstract: The use of bottom-up approaches to construct patterned surfaces for technological applications is appealing, but to date is applicable to only relatively small areas (approximately 10 square micrometers). We constructed highly periodic patterns at macroscopic length scales, in the range of square millimeters, by combining self-assembly of disk-like porphyrin dyes with physical dewetting phenomena. The patterns consisted of equidistant 5-nanometer-wide lines spaced 0.5 to 1 micrometers apart, forming single porphyrin stacks containing millions of molecules, and were formed spontaneously upon drop-casting a solution of the molecules onto a mica surface. On glass, thicker lines are formed, which can be used to align liquid crystals in large domains of square millimeter size.
