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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
Published on: June 10, 2021
Organic planar π-conjugated anions enable structural design of anion-π+ NIR-II phototheranostic agents
Ying Zhang1, Mingyang Han1, Guoyu Jiang2
1College of Chemistry and Chemical Engineering, Institute of Green Chemistry and Environment, Institutes of Biomedical Sciences, Inner Mongolia Key Laboratory of Synthesis and Application of Organic Functional Molecules, Inner Mongolia University, Hohhot, P. R. China.
Abstract:
Anion-π+ phototheranostic agents (PTAs) have attracted considerable interest for their exceptional luminescence and reactive oxygen species (ROS). However, current development is constrained by limited structural diversity and lack of second near-infrared (NIR-II) emission and photothermal performance, with the role of organic π-conjugated anions remaining unexplored. Here, we propose an organic π-conjugated anion-exchange strategy to construct advanced NIR-II PTAs. DTPAP-2B (with Br-) and DTPAP-2P (with pentacyanocyclopentadiene anion ((CCN)5-)), were synthesized. Upon nanoformulation, DTPAP-2P NPs exhibit pronounced absorption redshift, intense NIR-II emission, a large Stokes shift (340 nm), superior ROS generation, and high photothermal conversion efficiency (72%) compared to DTPAP-2B NPs. Single-crystal and theoretical analyses reveal that the planar (CCN)5- anion enhances dual anion-π+ interactions, promoting intramolecular charge transfer while suppressing intermolecular π-π stacking. This enables high-resolution NIR-II angiography and effective NIR-II imaging-guided synergistic photodynamic/photothermal therapy in female mice model. This work establishes organic π-conjugated anion exchange as a powerful strategy for developing robust NIR-II PTAs.
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