Work

Influence of Sequence Structure of Donor/Acceptor‐Containing Segment on Crystallization‐Driven Self‐Assembly Behavior and Photocatalytic Hydrogen Evolution Activity

Year: 2025

Type: article

Abstract: Crystallization‐driven self‐assembly (CDSA) has emerged as a facile strategy to generate donor‐acceptor (D‐A) π‐conjugated nanofibers with potential applications from photocatalysis to nanomedicine. However, the reports on CDSA of D‐A π‐conjugated‐polymer‐based block copolymers (BCPs) are rather rare. In this context, we report two types of BCPs containing the same corona‐forming poly( N ‐isopropylacrylamide) segment, but different core‐forming D‐A π‐conjugated blocks, one of which (BT‐OPE 5 ‐BT) contains an OPE 5 segment flanked by two electron‐deficient benzothiadiazole (BT) unit and another one of which (B‐ alt ‐BT) contains four phenylene (B) units and three BT units placed in an alternate way. The BT‐OPE 5 ‐BT‐based seed micelles were not kinetically frozen with obvious micellar dissolution at room temperature, whereas almost no micellar dissolution occurred for B‐ alt ‐BT‐based seed micelles. However, only polydisperse fiber‐like micelles can be formed by self‐seeding approach owing to presence of multiple packing modes for B‐ alt ‐BT‐ b ‐PNIPAM 36 over the micellar elongation. The B‐ alt ‐BT exhibited much more pronounced intra/intermolecular charge transfer effect than BT‐OPE 5 ‐BT, and thus the micelles of B‐ alt ‐BT‐ b ‐PNIPAM 36 exhibited about 50 nm red‐shift in UV/vis absorption band than that of BT‐OPE 5 ‐BT‐ b ‐PNIPAM 36 and appealing photocatalytic hydrogen evolution activities. This work highlights the importance of sequence structure of D/A units of D‐A segments on both CDSA behavior and photophysical/ chemical properties.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202501769

Authors: Fengfeng Huang, Yunuo Song, Yanhua Cheng, Guolin Lu, Xiaoyu Huang, Chun Feng