Tuning the Porosity and Photocatalytic Performance of Triazine-Based Graphdiyne Polymers through Polymorphism.

Crystalline and amorphous organic materials are an emergent class of heterogeneous photocatalysts for the generation of hydrogen from water, but a direct correlation between their structures and the resulting properties has not been achieved so far. To make a meaningful comparison between structurally different, yet chemically similar porous polymers, two porous polymorphs of a triazine-based graphdiyne (TzG) framework are synthesized by a simple, one-pot homocoupling polymerization reaction using as catalysts Cu for TzG and Pd /Cu for TzG . The polymers form through irreversible coupling reactions and give rise to a crystalline (TzG ) and an amorphous (TzG ) polymorph.

Exploring the "Goldilocks Zone" of Semiconducting Polymer Photocatalysts by Donor-Acceptor Interactions.

Water splitting using polymer photocatalysts is a key technology to a truly sustainable hydrogen-based energy economy. Synthetic chemists have intuitively tried to enhance photocatalytic activity by tuning the length of π-conjugated domains of their semiconducting polymers, but the increasing flexibility and hydrophobicity of ever-larger organic building blocks leads to adverse effects such as structural collapse and inaccessible catalytic sites. To reach the ideal optical band gap of about 2.

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.

Tailored Band Gaps in Sulfur- and Nitrogen-Containing Porous Donor-Acceptor Polymers.

Donor-acceptor dyads hold the key to tuning of electrochemical properties and enhanced mobility of charge carriers, yet their incorporation into a heterogeneous polymer network proves difficulty owing to the fundamentally different chemistry of the donor and acceptor subunits. A family of sulfur- and nitrogen-containing porous polymers (SNPs) are obtained via Sonogashira-Hagihara cross-coupling and combine electron-withdrawing triazine (C N ) and electron-donating, sulfur-containing linkers. Choice of building blocks and synthetic conditions determines the optical band gap (from 1.