EDOT-based conjugated polymers accessed via C-H direct arylation for efficient photocatalytic hydrogen production.

3,4-Ethylene dioxythiophene (EDOT), as a monomer of commercial conductive poly(3,4-ethylene dioxythiophene) (PEDOT), has been facilely incorporated into a series of new π-conjugated polymer-based photocatalysts, i.e., BSO2-EDOT, DBT-EDOT, Py-EDOT and DFB-EDOT, through atom-economic C-H direct arylation polymerization (DArP). The photocatalytic hydrogen production (PHP) test shows that donor-acceptor (D-A)-type BSO2-EDOT renders the highest hydrogen evolution rate (HER) among the linear conjugated polymers (CPs) ever reported. A HER up to 0.95 mmol h-1/6 mg under visible light irradiation and an unprecedented apparent quantum yield of 13.6% at 550 nm are successfully achieved. Note that the photocatalytic activities of the C-H/C-Br coupling-derived EDOT-based CPs are superior to those of their counterparts derived from the classical C-Sn/C-Br Stille coupling, demonstrating that EDOT is a promising electron-rich building block which can be facilely integrated into CP-based photocatalysts. Systematic studies reveal that the enhanced water wettability by the integration of polar BSO2 with hydrophilic EDOT, the increased electron-donating ability by O-C p-π conjugation, the improved electron transfer by D-A architecture, broad light harvesting, and the nano-sized colloidal character in a H2O/NMP mixed solvent rendered BSO2-EDOT as one of the best CP photocatalysts toward PHP.

Correction: EDOT-based conjugated polymers accessed via C-H direct arylation for efficient photocatalytic hydrogen production.

[This corrects the article DOI: 10.1039/D1SC05784G.].

Novel Diketopyrrolopyrrole-Based π-Conjugated Molecules Synthesized Via One-Pot Direct Arylation Reaction.

Diketopyrrolopyrrole (DPP) is an important type of π-conjugated building block for high-performance organic electronic materials. DPP-based conjugated materials are usually synthesized via Suzuki, Stille, or Negishi cross-coupling reactions, which require organometallic precursors. In this paper, a series of novel phenyl-cored DPP molecules, including five meta-phenyl-cored molecules and four para-phenyl-cored molecules, have been synthesized in moderate to good yields, in a facile manner, through the Pd-catalyzed direct arylation of C-H bonds, and their optoelectrical properties have been investigated in detail. All new molecules have been fully characterized by NMR, MALDI-TOF MS, elemental analysis, UV-visible spectroscopy, and cyclic voltammetry. This synthetic strategy has evident advantages of atom- and step-economy and low cost, compared with traditional cross-coupling reactions.