The development of supramolecular hosts which can efficiently encapsulate photosensitizers to improve the photodynamic efficacy holds great promise for cancer therapy. Here, we report two perylene diimide-based metallacages that can form stable host–guest complexes with planar conjugated molecules including polycyclic aromatic hydrocarbons and photosensitizers (hypocrellin A). Such host–guest complexation not only prevents the aggregation of photosensitizers in aqueous environments, but also offers fluorescence resonance energy transfer (FRET) from the metallacage to the photosensitizers to further improve the singlet oxygen generation (Φ_Δ = 0.66). The complexes are further assembled with amphiphilic polymers, forming nanoparticles with improved stability for anticancer study. Both in vitro and in vivo studies indicate that the nanoparticles display excellent anticancer activities upon light irradiation, showing great potential for cancer photodynamic therapy. This study provides a straightforward and effective approach for enhancing the photosensitivity of conventional photosensitizers via host–guest complexation-based FRET, which will open a new avenue for host–guest chemistry-based supramolecular theranostics.

开发能够有效封装光敏剂以提高光动力功效的超分子宿主为癌症治疗带来了巨大的希望。在这里，我们报道了两种基于苝二酰亚胺的金属络合物，它们可以与平面共轭分子（包括多环芳烃和光敏剂（竹红菌素A））形成稳定的主客体复合物。这种主客体络合不仅可以防止水环境中光敏剂的聚集，而且还提供从金属笼到光敏剂的荧光共振能量转移（FRET），以进一步提高单线态氧的生成（Φ _Δ = 0.66 ）。该复合物进一步与两亲性聚合物组装，形成具有更高稳定性的纳米颗粒，用于抗癌研究。体外和体内研究表明，纳米粒子在光照射下表现出优异的抗癌活性，显示出癌症光动力治疗的巨大潜力。这项研究提供了一种直接有效的方法，通过基于主客体络合的 FRET 增强传统光敏剂的光敏性，这将为基于主客体化学的超分子治疗诊断学开辟一条新途径。