Tunable Donor–Acceptor Linear Conjugated Polymers Involving Cyanostyrylthiophene Linkages for Visible-Light-Driven Hydrogen Production

In this paper, an atom- and step-economic direct C-H arylation polymerization (DArP) strategy was developed to access cyanostyrylthiophene (CST)-based donor–acceptor (D–A) conjugated polymers (CPs) used for photocatalytic hydrogen production (PHP) from water reduction. The new CST-based CPs CP1–CP5 with varied building blocks were systematically studied by X-ray single-crystal analysis, FTIR, scanning electron microscopy, UV-vis, photoluminescence, transient photocurrent response, cyclic voltammetry measurements, and a PHP test, which showed that the phenyl-cyanostyrylthiophene-based CP3 exhibits a superior hydrogen evolution rate (7.60 mmol h(−1) g(−1)) compared to other conjugated polymers. The structure–property–performance correlation results obtained in this study will provide an important guideline for the rational design of high-performance D–A CPs for PHP applications.