Hexakis Porphyrinato Benzenes. A New Class of Porphyrin Arrays

Abstract

A new type of porphyrin array has been synthesized by the coupling of six porphyrin moieties to a central benzene core via an ether linkage. The resulting porphryin supermolecule has a diameter up to 80 Å and a mass of 8500 daltons. In solution, the six porphyrins around the central benzene ring arrange themselves into three sets of offset overlapping dimers, which are rapidly interconverting at room temperature. Solution UV-vis and fluorescence studies, however, indicate that there are no electronic interactions between the individual porphyrin molecules. Upon spreading a chloroform solution of these porphyrin molecules on a surface, they self-assemble to form ring-shaped architectures on a micrometer scale. Near-field scanning optical microscopy studies reveal that the porphyrin moieties within the rings have an ordered arrangement with respect to their position in the ring after the sample has been annealed at 80 °C for 2 days.

Nanorings and rods interconnected by self-assembly mimicking an artificial network of neurons

“…It is important to mention here that the spontaneous formation of rings by self-assembly has been scarcely reported. Most of the reported structures follow formation mechanisms derived from de-wetting processes in which either the spontaneous formation of pinholes, 2D bubbles, the concentric accumulation of material mediated by local capillarity (coffee-stain effect) or Marangoni-flow engineering produce rings on flat surfaces [38][39][40][41][42][43][44] . However, none of the latter mechanisms can explain the formation of the rings for derivatives 4 that are interconnected in a neural network fashion both on flat surfaces and inside a polymeric matrix.…”

Molecular Materials by Self‐Assembly of Porphyrins, Phthalocyanines, and Perylenes

“…8A). [27] With a specifically designed low-current STM, assemblies of the porphyrin hexamers could be imaged with submolecular resolution at the interface of highly oriented pyrolytic graphite (HOPG) and 1-phenyloctane. [28] The free base hexamer 12 was found to adsorb to the surface in two orientations, i.e., 'face-on' as single molecules and 'edge-on' in the form of stacks, of which the latter arrangement was the most thermodynamically stable.…”

Aided Self‐Assembly of Porphyrin Nanoaggregates into Ring‐Shaped Architectures

“…As part of our efforts to construct functional architectures, we have synthesized oligomeric porphyrin arrays 1 and 2 (Figure 1), which can form large rings on solid substrates as we have previously reported [14] and are able to form stable p-stacked columnar arrays at an air±water interface. [15] The extended p-surface in combination with their disk-like shape makes them self-assemble in solution into columnar stacks.…”