Fluorescent Sulphur- and Nitrogen-Containing Porous Polymers with Tuneable Donor-Acceptor Domains for Light-Driven Hydrogen Evolution.

Light-driven water splitting is a potential source of abundant, clean energy, yet efficient charge-separation and size and position of the bandgap in heterogeneous photocatalysts are challenging to predict and design. Synthetic attempts to tune the bandgap of polymer photocatalysts classically rely on variations of the sizes of their π-conjugated domains. However, only donor-acceptor dyads hold the key to prevent undesired electron-hole recombination within the catalyst via efficient charge separation. Building on our previous success in incorporating electron-donating, sulphur-containing linkers and electron-withdrawing, triazine (C3 N3 ) units into porous polymers, we report the synthesis of six visible-light-active, triazine-based polymers with a high heteroatom-content of S and N that photocatalytically generate H2 from water: up to 915 µmol h-1 g-1 with Pt co-catalyst, and-as one of the highest to-date reported values -200 µmol h-1 g-1 without. The highly modular Sonogashira-Hagihara cross-coupling reaction we employ, enables a systematic study of mixed (S, N, C) and (N, C)-only polymer systems. Our results highlight that photocatalytic water-splitting does not only require an ideal optical bandgap of ≈2.2 eV, but that the choice of donor-acceptor motifs profoundly impacts charge-transfer and catalytic activity.

Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly.

We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters.