Photocaged Perylene Diimide Precursor for Precise Solubility Control and High-Quality Film Fabrication

作者团队：Yinan Sun, Qinglin Jiang* (通讯), Yanuo Zhu, Wenle Tan, Bohan Wang, Jiaji Yang, Changhao Ruan, Yuguang Ma* (通讯)

作者单位：Institute of Polymer Optoelectronic Materials and Devices, Guangdong Basic Research Center of Excellence for Energy and Information Polymer Materials, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (Guangzhou, P. R. China); Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology (Guangzhou, P. R. China)

通讯作者邮箱：jiangql@scut.edu.cn; ygma@scut.edu.cn

发表时间：2025-07-15

期刊卷期：Small, Volume 21, Issue 36, Article ID: 2506103

DOI：10.1002/smll.202506103

The inherent contradiction between solubility and electronic properties remains a key challenge limiting the wide application of perylene diimides (PDIs). Here, a novel photocaged precursor strategy is proposed to realize precise solubility transitions by photo-control and to prepare insoluble PDI films directly by irradiating the solution without additional thermal or chemical post-processing.

To this end, a specifically designed soluble PDI precursor, N, N’-di-5-(dodecyloxy)-2-nitrobenzyl acetate-3, 4, 9, 10-perylenetetracarboxylic diimide, is synthesized by linking solubilizing chains to the imide-position via photocleavable o-nitrobenzyl (ONB) photocaged group. Upon irradiation at 365 nm, the ONB-linker breaks effectively, removing the solubilizing chains precisely and yielding an insoluble PDI derivative.

Spectroscopy results reveal that the photocleavable behavior is effective in both solution and solid states (>76% conversion within 600 s in solution). High-quality insoluble PDI films with favorable flatness and continuity (surface roughness 2.8 nm) and promising conductivity (3.7 × 10⁻² S cm⁻¹ after chemical doping) are prepared directly in solution by irradiation.

This study establishes, for the first time, a universal and spatiotemporally controllable strategy for the direct preparation of insoluble PDI film, offering a new idea for balancing the solubility and charge transport properties, and a potential guideline for solution processing of high-performance, low-solubility organic semiconductors.

direct photo-deposition perylene diimide photocaged precursor photo-induced solubility transition solution processing

• National Natural Science Foundation of China (Grant Numbers: 52203221, 92463310)
• National Key Research and Development Program of China (Grant Number: 2020YFA0714604)
• Guangdong Provincial Quantum Science Strategic Initiative (Grant Number: GDZX2301002)
• Science and Technology Projects in Guangzhou (Grant Number: 2024A04J2529)
• Young Talent Support Project of Guangzhou Association for Science and Technology (Grant Number: QT2024-001)
• Fundamental Research Funds of State Key Laboratory of Luminescent Materials and Devices (Grant Numbers: Skllmd-2023-03, Skllmd-2024-23, Skllmd-2024-18)
• Songshan Lake Materials Laboratory (Grant Number: 2023SLABFK05)
• Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology (Grant Number: 2023B1212060003)

原文链接（Wiley Online Library）：点击访问文献原文