Hybrid Nanocrystals of Small Molecules and Chemically Disordered Polymers.

Organic crystals formed by small molecules can be highly functional but are often brittle or insoluble structures with limited possibilities for use or processing from a liquid phase. A possible solution is the nanoscale integration of polymers into organic crystals without sacrificing long-range order and therefore function. This enables the organic crystals to benefit from the advantageous mechanical and chemical properties of the polymeric component. We report here on a strategy in which small molecules cocrystallize with side chains of chemically disordered polymers to create hybrid nanostructures containing a highly ordered lattice. Synchrotron X-ray scattering, absorption spectroscopy, and coarse-grained molecular dynamics simulations reveal that the polymer backbones form an "exo-crystalline" layer of disordered chains that wrap around the nanostructures, becoming a handle for interesting properties. The morphology of this "hybrid bonding polymer" nanostructure is dictated by the competition between the polymers' entropy and the enthalpy of the lattice allowing for control over the aspect ratio of the nanocrystal by changing the degree of polymer integration. We observed that nanostructures with an exo-crystalline layer of polymer exhibit enhanced fracture strength, self-healing capacity, and dispersion in water, which benefits their use as light-harvesting assemblies in photocatalysis. Guided by computation, future work could further explore these hybrid nanostructures as components for functional materials.

Photocatalytic Aqueous CO2 Reduction to CO and CH4 Sensitized by Ullazine Supramolecular Polymers.

There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO2 reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO2 photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH4 comparable to those obtained with a precious metal-based [Ru(phen)3](PF6)2 sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production.

The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. We investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 µm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ∼110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.

Imaging Supramolecular Morphogenesis with Confocal Laser Scanning Microscopy at Elevated Temperatures.

The morphogenesis of supramolecular assemblies is a highly dynamic process that has only recently been recognized, and our understanding of this phenomenon will require imaging techniques capable of crossing scales. Shape transformations depend both on the complex energy landscapes of supramolecular systems and the kinetically controlled pathways that define their structures and functions. We report here the use of confocal laser scanning microscopy coupled with a custom-designed variable-temperature sample stage that enables in situ observation of such shape changes. The submicrometer resolution of this technique allows for real-time observation of the nanostructures in the native liquid environments in which they transform with thermal energy. We use this technique to study the temperature-dependent morphogenic behavior of peptide amphiphile nanofibers and photocatalytic chromophore amphiphile nanoribbons. The variable-temperature confocal microscopy technique demonstrated in this work can sample a large volume and provides real-time information on thermally induced morphological changes in the solution.

Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation.

The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. We investigated here the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10-15 kJ·mol-1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H2 production.

Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds.

The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.