Organic planar π-conjugated anions enable structural design of anion-π<sup>+</sup> NIR-II phototheranostic agents.
basic_science · Level V
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- Record sourced from PubMed, PMID 42420266.
- Also identified by DOI 10.1038/s41467-026-75247-7.
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Abstract
Anion-π<sup>+</sup> 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<sup>-</sup>) and DTPAP-2P (with pentacyanocyclopentadiene anion ((CCN)<sub>5</sub><sup>-</sup>)), 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)<sub>5</sub><sup>-</sup> anion enhances dual anion-π<sup>+</sup> 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.