Bimolecular Sandwich Aggregates of Porphyrin Nanorings.

Extended π-systems often form supramolecular aggregates, drastically changing their optical and electronic properties. However, aggregation processes can be difficult to characterize or predict. Here, we show that butadiyne-linked 8- and 12-porphyrin nanorings form stable and well-defined bimolecular aggregates with remarkably sharp NMR spectra, despite their dynamic structures and high molecular weights (12.7 to 26.0 kDa). Pyridine breaks up the aggregates into their constituent rings, which are in slow exchange with the aggregates on the NMR time scale. All the aggregates have the same general two-layer sandwich structure, as deduced from NMR spectroscopy experiments, including 1H DOSY, 1H-1H COSY, TOCSY, NOESY, and 1H-13C HSQC. This structure was confirmed by analysis of residual dipolar couplings from 13C-coupled 1H-13C HSQC experiments on one of the 12-ring aggregates. Variable-temperature NMR spectroscopy revealed an internal ring-on-ring rotation process by which two π-π stacked conformers interconvert via a staggered conformation. A slower dynamic process, involving rotation of individual porphyrin units, was also detected by exchange spectroscopy in the 8-ring aggregates, implying partial disaggregation and reassociation. Molecular dynamics simulations indicate that the 8-ring aggregates are bowl-shaped and highly fluxional, compared to the 12-ring aggregates, which are cylindrical. This work demonstrates that large π-systems can form surprisingly well-defined aggregates and may inspire the design of other noncovalent assemblies.

Template-Directed Synthesis of Strained meso-meso-Linked Porphyrin Nanorings.

Strained macrocycles display interesting properties, such as conformational rigidity, often resulting in enhanced π-conjugation or enhanced affinity for non-covalent guest binding, yet they can be difficult to synthesize. Here we use computational modeling to design a template to direct the formation of an 18-porphyrin nanoring with direct meso-meso bonds between the porphyrin units. Coupling of a linear 18-porphyrin oligomer in the presence of this template gives the target nanoring, together with an unexpected 36-porphyrin ring by-product. Scanning tunneling microscopy (STM) revealed the elliptical conformations and flexibility of these nanorings on a Au(111) surface.

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.