Accelerated Discovery of Organic Polymer Photocatalysts for Hydrogen Evolution from Water through the Integration of Experiment and Theory.

Conjugated polymers are an emerging class of photocatalysts for hydrogen production where the large breadth of potential synthetic diversity presents both an opportunity and a challenge. Here, we integrate robotic experimentation with high-throughput computation to navigate the available structure-property space. A total of 6354 co-polymers was considered computationally, followed by the synthesis and photocatalytic characterization of a sub-library of more than 170 co-polymers.

The simplest supramolecular helix.

Diethylamine is the smallest and simplest molecule that features a supramolecular helix as its lowest energy aggregate. Structural studies and large scale sampling simulations show that the helical arrangement is more stable than cyclic structures, which are the dominant species for other small hydrogen bonding molecules.

Functional materials discovery using energy-structure-function maps.

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail.

Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO, but is much more active under visible light.

Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light.

A perylene diimide rotaxane: synthesis, structure and electrochemically driven de-threading.

The first example of a [2]-rotaxane in which a perylene diimide acts as a recognition site has been synthesised and characterised. The interlocked nature of the compound has been verified by both NMR studies and an X-ray structure determination. Electrochemical investigations confirm that the nature of the redox processes associated with the perylene diimide are modified by the complexation process and that it is possible to mono-reduce the [2]-rotaxane to give a radical anion based rotaxane.