Bending a photonic wire into a ring.

Natural light-harvesting systems absorb sunlight and transfer its energy to the reaction centre, where it is used for photosynthesis. Synthetic chromophore arrays provide useful models for understanding energy migration in these systems. Research has focused on mimicking rings of chlorophyll molecules found in purple bacteria, known as 'light-harvesting system 2'. Linear meso-meso linked porphyrin chains mediate rapid energy migration, but until now it has not been possible to bend them into rings. Here we show that oligo-pyridyl templates can be used to bend these rod-like photonic wires to create covalent nanorings that consist of 24 porphyrin units and a single butadiyne link. Their elliptical conformations have been probed by scanning tunnelling microscopy. This system exhibits two excited state energy transfer processes: one from a bound template to the peripheral porphyrins and one, in the template-free ring, from the exciton-coupled porphyrin array to the π-conjugated butadiyne-linked porphyrin dimer segment.

Self-assembly of a strapped linear porphyrin oligomer on HOPG.

Polymeric structures based on porphyrin units exhibit a range of complex properties, such as nanoscale charge transport and quantum interference effects, and have the potential to act as biomimetic materials for light-harvesting and catalysis. These functionalities are based upon the characteristics of the porphyrin monomers, but are also emergent properties of the extended polymer system. Incorporation of these properties within solid-state devices requires transfer of the polymers to a supporting substrate, and may require a high-degree of lateral order. Here we show that highly ordered self-assembled structures can be formed via a simple solution deposition protocol; for a strapped linear porphyrin oligomer adsorbed on a highly oriented pyrolytic graphite (HOPG) substrate. Two distinct molecule-molecule interactions are observed to drive the formation of two molecular phases ('Interdigitated' and 'Bridge-stabilised') characterised by scanning tunnelling microscopy, providing information on the unit cell dimensions and self-assembled structure. The concentration dependence of these phases is investigated, and we conclude that the bridge-stabilised phase is a thermodynamically stable structure at room temperature.