Aggregation plays a critical role in modulating the photophysical process of organic molecules. However, the rational control of the construction of a function-oriented stacking mode for efficient photothermal (PT) conversion in the second near-infrared region (NIR-II; 1000–1700 nm) remains a challenge. Herein, an H-aggregation of 3,3′,5,5′-Tetramethylbenzidine (TMB)–TMB dication (TMB⁺⁺) complexes in linear agarose (H-TTC/LAG) with narrowed band gap (0.96 eV) was fabricated through intermolecular hydrogen-bonding interactions between the amino groups of TTC and the peripheral hydroxyl groups of LAG. Charge-transfer mechanism and H-aggregation ensured NIR-II absorption of the complex at >1400 nm. The H-aggregation also promoted a non-radiation relaxation pathway and improved the thermal stability of TTC, which together favored the constructed H-TTC/LAG with ultra-efficient PT conversion that increased rapidly to 140 °C in 15 s under the NIR-II laser (1064 nm, 1.0 W cm⁻²) irradiation. Such a unique H-TTC/LAG with good biocompatibility was used to demonstrate a superior PT therapy via high-efficiency tumor growth inhibition in mouse mammary carcinoma (4T1) the BALB/c mice tumor-bearing xenografts. This is the first established H-aggregation of charge-transfer complexes in a noncovalent system, which not only provides a new strategy to develop ultra-efficient NIR-II PT materials but also paves the way for constructing functional materials with aggregates of charge-transfer complexes.

聚集在调节有机分子的光物理过程中起着关键作用。然而，在第二近红外区域（NIR-II；1000-1700 nm）中合理控制构建面向功能的堆叠模式以实现有效的光热（PT）转换仍然是一个挑战。在此，3,3',5,5'-四甲基联苯胺（TMB）-TMB 阳离子（TMB ⁺⁺) 线性琼脂糖 (H-TTC/LAG) 中带隙变窄 (0.96 eV) 的复合物是通过 TTC 的氨基和 LAG 的外围羟基之间的分子间氢键相互作用制造的。电荷转移机制和 H 聚集确保了复合物在 >1400 nm 处的 NIR-II 吸收。H-聚集还促进了非辐射弛豫途径并提高了 TTC 的热稳定性，这共同有利于构建的 H-TTC/LAG 具有超高效的 PT 转换，在 NIR-下 15 秒内迅速增加到 140°C。 II 激光（1064 nm，1.0 W cm ^-2) 辐照。这种具有良好生物相容性的独特 H-TTC/LAG 用于通过高效抑制小鼠乳腺癌 (4T1) BALB/c 小鼠荷瘤异种移植瘤的肿瘤生长来证明优越的 PT 治疗。这是第一个在非共价体系中建立的电荷转移复合物的 H 聚集，它不仅为开发超高效 NIR-II PT 材料提供了新策略，而且为构建具有电荷转移聚集体的功能材料铺平了道路。复合体。