Molecular Quantum Rings Formed from a π-Conjugated Macrocycle.

The electronic structure of a molecular quantum ring (stacks of 40-unit cyclic porphyrin polymers) is characterized via scanning tunneling microscopy and scanning tunneling spectroscopy. Our measurements access the energetic and spatial distribution of the electronic states and, utilizing a combination of density functional theory and tight-binding calculations, we interpret the experimentally obtained electronic structure in terms of coherent quantum states confined around the circumference of the π-conjugated macrocycle. These findings demonstrate that large (53 nm circumference) cyclic porphyrin polymers have the potential to act as molecular quantum rings.

A Coarse-Grained Model for Free and Template-Bound Porphyrin Nanorings.

Coarse-grained simulation models are developed to study both template-bound and free porphyrin nanoring systems. Key interactions are modeled with relatively simple (and physically motivated) energy functions which allow for relatively facile transfer both between different ring sizes and between the template-bound and free nanoring systems. The effects of varying the model parameters on the respective radii of gyration are determined. The effects of including different templates on the ring structure are investigated both in terms of the detailed geometry of the template and the interaction strength between the template and the metal centers in the nanorings. The role of the template-nanoring interaction strength in controlling potential "caterpillar track" rotational motion is discussed. The relationship of the model to experimental small-angle X-ray, exchange spectroscopy, and electron spin resonance results is discussed.

Vernier templating and synthesis of a 12-porphyrin nano-ring.

Templates are widely used to arrange molecular components so they can be covalently linked into complex molecules that are not readily accessible by classical synthetic methods. Nature uses sophisticated templates such as the ribosome, whereas chemists use simple ions or small molecules. But as we tackle the synthesis of larger targets, we require larger templates-which themselves become synthetically challenging. Here we show that Vernier complexes can solve this problem: if the number of binding sites on the template, n(T), is not a multiple of the number of binding sites on the molecular building blocks, n(B), then small templates can direct the assembly of relatively large Vernier complexes where the number of binding sites in the product, n(P), is the lowest common multiple of n(B) and n(T) (refs 8, 9). We illustrate the value of this concept for the covalent synthesis of challenging targets by using a simple six-site template to direct the synthesis of a 12-porphyrin nano-ring with a diameter of 4.7 nm, thus establishing Vernier templating as a powerful new strategy for the synthesis of large monodisperse macromolecules.

Caterpillar track complexes in template-directed synthesis and correlated molecular motion.

Small alterations to the structure of a star-shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8- and 10-porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10-porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates.

Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring.

Vernier templating exploits a mismatch between the number of binding sites in a template and a reactant to direct the formation of a product that is large enough to bind several template units. Here, we present a detailed study of the Vernier-templated synthesis of a 12-porphyrin nanoring. NMR and small-angle X-ray scattering (SAXS) analyses show that Vernier complexes are formed as intermediates in the cyclo-oligomerization reaction. UV/Vis/NIR titrations show that the three-component assembly of the 12-porphyrin nanoring figure-of-eight template complex displays high allosteric cooperativity and chelate cooperativity. This nanoring-template 1:2 complex is among the largest synthetic molecules to have been characterized by single-crystal analysis. It crystallizes as a racemate, with an angle of 27° between the planes of the two template units. The crystal structure reveals many unexpected intramolecular C-H⋅⋅⋅N contacts involving the tert-butyl side chains. Scanning tunneling microscopy (STM) experiments show that molecules of the 12-porphyrin template complex can remain intact on the gold surface, although the majority of the material unfolds into the free nanoring during electrospray deposition.

Mechanical stiffening of porphyrin nanorings through supramolecular columnar stacking.

Solvent-induced aggregates of nanoring cyclic polymers may be transferred by electrospray deposition to a surface where they adsorb as three-dimensional columnar stacks. The observed stack height varies from single rings to four stacked rings with a layer spacing of 0.32 ± 0.04 nm as measured using scanning tunneling microscopy. The flexibility of the nanorings results in distortions from a circular shape, and we show, through a comparison with Monte Carlo simulations, that the bending stiffness increases linearly with the stack height. Our results show that noncovalent interactions may be used to control the shape and mechanical properties of artificial macromolecular aggregates offering a new route to solvent-induced control of two-dimensional supramolecular organization.

Cyclodextrin-templated porphyrin nanorings.

α- and ß-cyclodextrins have been used as scaffolds for the synthesis of six- and seven-legged templates by functionalizing every primary CH2OH with a 4-pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α-cyclodextrin-based template within the six-porphyrin nanoring (74 M) is almost as high as for the previously studied rigid hexadentate template (180 M). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template-directed synthesis of larger macrocycles.

Amplified two-photon absorption in trans-A2B2-porphyrins bearing nitrophenylethynyl substituents.

We show that peripheral nitro groups enhance the maximum two-photon absorption cross-section of trans-A(2)B(2)-porphyrins bearing two phenylethynyl substituents by more than one order of magnitude. Maximum values as high as 1000 GM result from realization of suitable conditions for effective resonance enhancement along with a lowering of the energy and intensification of the two-photon allowed transitions in the Soret region.

Linear and cyclic porphyrin hexamers as near-infrared emitters in organic light-emitting diodes.

Here we report organic light-emitting diodes incorporating linear and cyclic porphyrin hexamers which have red-shifted emission (λ(PL) = 873 and 920 nm, respectively) compared to single porphyrin rings as a consequence of their extended π-conjugation. We studied the photoluminescence and electroluminescence of blends with poly(9,9'-dioctylfluorene-alt-benzothiadiazole), demonstrating a high photoluminescence quantum efficiency of 7.7% for the linear hexamer when using additives to prevent aggregation and achieving high color purity near-infrared electroluminescence.

Belt-shaped π-systems: relating geometry to electronic structure in a six-porphyrin nanoring.

Linear π-conjugated oligomers have been widely investigated, but the behavior of the corresponding cyclic oligomers is poorly understood, despite the recent synthesis of π-conjugated macrocycles such as [n]cycloparaphenylenes and cyclo[n]thiophenes. Here we present an efficient template-directed synthesis of a π-conjugated butadiyne-linked cyclic porphyrin hexamer directly from the monomer. Small-angle X-ray scattering data show that this nanoring is shape-persistent in solution, even without its template, whereas the linear porphyrin hexamer is relatively flexible. The crystal structure of the nanoring-template complex shows that most of the strain is localized in the acetylenes; the porphyrin units are slightly curved, but the zinc coordination sphere is undistorted. The electrochemistry, absorption, and fluorescence spectra indicate that the HOMO-LUMO gap of the nanoring is less than that of the linear hexamer and less than that of the corresponding polymer. The nanoring exhibits six one-electron reductions and six one-electron oxidations, most of which are well resolved. Ultrafast fluorescence anisotropy measurements show that absorption of light generates an excited state that is delocalized over the whole π-system within a time of less than 0.5 ps. The fluorescence spectrum is amazingly structured and red-shifted. A similar, but less dramatic, red-shift has been reported in the fluorescence spectra of cycloparaphenylenes and was attributed to a high exciton binding energy; however the exciton binding energy of the porphyrin nanoring is similar to those of linear oligomers. Quantum-chemical excited state calculations show that the fluorescence spectrum of the nanoring can be fully explained in terms of vibronic Herzberg-Teller (HT) intensity borrowing.

On-Surface Synthesis within a Porphyrin Nanoring Template.

On-surface synthesis provides a route for the production of 1D and 2D covalently bonded polymeric structures. Such reactions are confined to the surface of a substrate and the catalytic properties of the substrate are often utilised to initiate the reaction. Recent studies have focused on the properties of various crystallographic planes of metallic substrates, as well as native surface features such as step-edges, in an effort to provide control over the pathway of the reaction and the resultant products. An alternative approach is to template the catalytic surface with a porous molecular overlayer; giving rise to well-defined surface regions within which an on-surface reaction may be confined. Here we present a methodology where macromolecular templates are used to confine an on-surface reaction. Cyclic porphyrin polymers, nanorings - consisting of 40 porphyrin units with internal diameter 13 nm, are used to form a template on a Au(111) surface, and an on-surface Ullmann-type coupling reaction is initiated within the nanoring template. The surface confined template and covalently coupled reaction products are investigated and characterised with scanning tunnelling microscopy.

Ordering, flexibility and frustration in arrays of porphyrin nanorings.

The regular packing of atoms, molecules and nanoparticles provides the basis for the understanding of structural order within condensed phases of matter. Typically the constituent particles are considered to be rigid with a fixed shape. Here we show, through a combined experimental and numerical study of the adsorption of cyclic porphyrin polymers, nanorings, on a graphite surface, that flexible molecules can exhibit a rich and complex packing behaviour. Depending on the number of porphyrin sub-units within the nanoring we observe either a highly ordered hexagonal phase or frustrated packing driven by directional interactions which for some arrangements is combined with the internal deformation of the cyclic polymer. Frustration and deformation occur in arrays of polymers with ten sub-units since close packing and co-alignment of neighbouring groups cannot be simultaneously realised for nanorings with this internal symmetry.

Nanorings with copper(ii) and zinc(ii) centers: forcing copper porphyrins to bind axial ligands in heterometallated oligomers.

The affinity of copper(ii) porphyrins for pyridine ligands is extremely weak, but oligo-pyridine templates can be used to direct the synthesis of Cu-containing cyclic porphyrin oligomers when they also have Zn centers. We report the synthesis of two heterometallated nanorings: a six-porphyrin ring prepared from a Zn/Cu/Zn linear trimer and a ten-porphyrin ring prepared from a Zn/Zn/Cu/Zn/Zn pentamer. Both these macrocycles have copper porphyrins at two specific positions across the diameter of the ring and zinc at other sites. The presence of a paramagnetic metal results in broadening of the 1H NMR spectra and reduces the relaxation time constants (T1 and T2). The changes in T1 provide quantitative information on the distance of each proton from the copper atom. The Zn/Zn/Cu/Zn/Zn linear porphyrin pentamer binds strongly to a penta-pyridyl template, despite the weakness of the Cu-N interaction, because of the chelate cooperativity of the neighboring Zn-N coordination. The stabilities of a family of four linear porphyrin pentamer complexes were determined by UV-vis-NIR titration and analyzed using a chemical double-mutant cycle. The results show that the free energy of interaction of a copper center to axial pyridine ligands is -6.2 kJ mol-1 when the entropy cost of bringing together the two molecules has already been paid by pyridine-zinc interactions. The development of template-directed approaches to the synthesis of nanorings with combinations of different metals at specific positions around the ring opens up many possibilities for controlling the photophysical behavior of these supramolecular systems and for probing their conformations by EPR.

Caterpillar Track Complexes in Template-Directed Synthesis and Correlated Molecular Motion.

Small alterations to the structure of a star-shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8- and 10-porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10-porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates.

Supramolecular nesting of cyclic polymers.

Advances in template-directed synthesis make it possible to create artificial molecules with protein-like dimensions, directly from simple components. These synthetic macromolecules have a proclivity for self-organization that is reminiscent of biopolymers. Here, we report the synthesis of monodisperse cyclic porphyrin polymers, with diameters of up to 21 nm (750 C­C bonds). The ratio of the intrinsic viscosities for cyclic and linear topologies is 0.72, indicating that these polymers behave as almost ideal flexible chains in solution. When deposited on gold surfaces, the cyclic polymers display a new mode of two-dimensional supramolecular organization, combining encapsulation and nesting; one nanoring adopts a near-circular conformation, thus allowing a second nanoring to be captured within its perimeter, in a tightly folded conformation. Scanning tunnelling microscopy reveals that nesting occurs in combination with stacking when nanorings are deposited under vacuum, whereas when they are deposited directly from solution under ambient conditions there is stacking or nesting, but not a combination of both.

Structure-Directed Exciton Dynamics in Templated Molecular Nanorings.

Conjugated polymers with cyclic structures are interesting because their symmetry leads to unique electronic properties. Recent advances in Vernier templating now allow large shape-persistent fully conjugated porphyrin nanorings to be synthesized, exhibiting unique electronic properties. We examine the impact of different conformations on exciton delocalization and emission depolarization in a range of different porphyrin nanoring topologies with comparable spatial extent. Low photoluminescence anisotropy values are found to occur within the first few hundred femtoseconds after pulsed excitation, suggesting ultrafast delocalization of excitons across the nanoring structures. Molecular dynamics simulations show that further polarization memory loss is caused by out-of-plane distortions associated with twisting and bending of the templated nanoring topologies.

Ultrafast delocalization of excitation in synthetic light-harvesting nanorings.

Rings of chlorophyll molecules harvest sunlight remarkably efficiently during photosynthesis in purple bacteria. The key to their efficiency lies in their highly delocalized excited states that allow for ultrafast energy migration. Here we show that a family of synthetic nanorings mimic the ultrafast energy transfer and delocalization observed in nature. π-Conjugated nanorings with diameters of up to 10 nm, consisting of up to 24 porphyrin units, are found to exhibit excitation delocalization within the first 200 fs of light absorption. Transitions from the first singlet excited state of the circular nanorings are dipole-forbidden as a result of symmetry constraints, but these selection rules can be lifted through static and dynamic distortions of the rings. The increase in the radiative emission rate in the larger nanorings correlates with an increase in static disorder expected from Monte Carlo simulations. For highly symmetric rings, the radiative rate is found to increase with increasing temperature. Although this type of thermally activated superradiance has been theoretically predicted in circular chromophore arrays, it has not previously been observed in any natural or synthetic systems. As expected, the activation energy for emission increases when a nanoring is fixed in a circular conformation by coordination to a radial template. These nanorings offer extended chromophores with high excitation delocalization that is remarkably stable against thermally induced disorder. Such findings open new opportunities for exploring coherence effects in nanometer molecular rings and for implementing these biomimetic light-harvesters in man-made devices.

Chromophores in Molecular Nanorings: When Is a Ring a Ring?

The topology of a conjugated molecule plays a significant role in controlling both the electronic properties and the conformational manifold that the molecule may explore. Fully π-conjugated molecular nanorings are of particular interest, as their lowest electronic transition may be strongly suppressed as a result of symmetry constraints. In contrast, the simple Kasha model predicts an enhancement in the radiative rate for corresponding linear oligomers. Here we investigate such effects in linear and cyclic conjugated molecules containing between 6 and 42 butadiyne-linked porphyrin units (corresponding to 600 C-C bonds) as pure monodisperse oligomers. We demonstrate that as the diameter of the nanorings increases beyond ∼10 nm, its electronic properties tend toward those of a similarly sized linear molecule as a result of excitation localization on a subsegment of the ring. However, significant differences persist in the nature of the emitting dipole polarization even beyond this limit, arising from variations in molecular curvature and conformation.

Height dependent molecular trapping in stacked cyclic porphyrin nanorings.

Stacked layers of cyclic porphyrin nanorings constitute nanoscale receptacles with variable height and diameter which preferentially adsorb sublimed molecules. Using scanning tunnelling microscopy we determine the filling capacity of these nanoring traps, and the dependence of adsorbate capture on stack height and diameter.