Tuning the Aggregates of Thiophene‐based Trimers by Methyl Side‐chain Engineering for Photocatalytic Hydrogen Evolution

Organic π‐conjugated semiconductors (OCSs) have recently emerged as a promising alternative to traditional inorganic materials for photocatalysis. However, the aggregation of OCSs in photocatalytic aqueous solution caused by self‐assembly, which closely relates to the photocatalytic activity, has no...

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Published in:Angewandte Chemie International Edition 2024-01, Vol.63 (1), p.e202315333-n/a
Main Authors: Yuan, Xiaojiao, Yang, Kunran, Grazon, Chloé, Wang, Cong, Vallan, Lorenzo, Isasa, Jean‐David, Resende, Pedro M., Li, Fanxing, Brochon, Cyril, Remita, Hynd, Hadziioannou, Georges, Cloutet, Eric, Li, Jian
Format: Article
Language:English
Subjects:
Aggregates
Aggregation
Aggregation behavior
Aqueous solutions
Carrier transport
Catalytic activity
Chemical Sciences
Current carriers
Hydrogen evolution
Hydrogen Production
Inorganic materials
Intramolecular Packing
Organic semiconductors
Photocatalysis
Self-assembly
Thiophene
Trimers
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Summary:Organic π‐conjugated semiconductors (OCSs) have recently emerged as a promising alternative to traditional inorganic materials for photocatalysis. However, the aggregation of OCSs in photocatalytic aqueous solution caused by self‐assembly, which closely relates to the photocatalytic activity, has not yet been studied. Here, the relationship between the aggregation of 4,7‐Bis(thiophen‐2‐yl) benzothiadiazole (TBT) and the photocatalytic activity was systematically investigated by introducing and varying the position of methyl side chains on the two peripheral thiophene units. Experimental and theoretical results indicated that the introduction of ‐CH3 group at the 3‐position of TBT resulted in the smallest size and best crystallinity of aggregates compared to that of TBT, 4‐ and 5‐positions. As a result, TBT‐3 exhibited an excellent photocatalytic activity towards H2 evolution, ascribed to the shorten charge carrier transport distance and solid long‐range order. These results suggest the important role of aggregation behavior of OCSs for efficient photocatalysis. The relationship between the aggregation of 4,7‐bis(thiophen‐2‐yl) benzothiadiazole (TBT)‐based conjugated trimers and their photocatalytic activity was systematically investigated by methyl side‐chain engineering. TBT‐3 with the smallest size of aggregates and highest crystallinity exhibit the highest photocatalytic H2 evolution activity, which is due to the shorter charge carrier transport distance and solid long‐range order.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202315333