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5283308 
Journal Article 
Photocatalytically active ladder polymers 
Vogel, A; Forster, M; Wilbraham, L; Smith, CL; Cowan, AJ; Zwijnenburg, MA; Sprick, RS; Cooper, AI 
2019 
Yes 
Faraday Discussions
ISSN: 1359-6640
EISSN: 1364-5498 
English 
30972395 
Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h-1 g-1) in comparison to that of cLaP2 (18 μmol h-1 g-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.