Post-synthetic modification with β-diketone has been proven as an effective strategy to improve the visible light response activities of metal-organic frameworks (MOFs). Nevertheless, the effects of the anchored-diketones on the excitonic behaviors and photocatalytic mechanisms of MOFs are still unclear. Herein, two MOFs (MIL-101 with Cr^III and MIL-101 with Al^III) were employed as prototypical materials to further understand this post-synthetic modification strategy. Diketone anchoring could enhance the photocatalytic generation of singlet oxygen (¹O₂) by the two MOFs in a joint mechanism: exciton-mediated energy transfer and photosensitization. Diketone anchoring induced triplet exciton was found playing an important role in the photocatalytic generation of ¹O₂. The photosensitization of the anchored-diketone also played a key role in the photocatalytic generation of ¹O₂. The results here provide a useful guidance for the development of MOFs-based photocatalysts and are helpful to realize the regulation of excitonic behaviors and photocatalytic mechanisms of MOFs.

β-二酮的合成后修饰已被证明是提高金属有机骨架（MOFs）可见光响应活性的有效策略。然而，锚定二酮对MOFs激子行为和光催化机制的影响仍不清楚。在此，两种 MOF（带有 Cr ^{III 的}MIL-101 和带有 Al ^{III 的}MIL-101 ）被用作原型材料，以进一步了解这种合成后的改性策略。二酮锚定可以增强单线态氧（¹ O ₂) 由两个 MOF 联合机制：激子介导的能量转移和光敏化。发现二酮锚定诱导的三重态激子在光催化生成¹ O _{2 中}起重要作用。锚定二酮的光敏化也在光催化生成¹ O _{2 中}发挥了关键作用。该研究结果为MOFs基光催化剂的开发提供了有益的指导，有助于实现MOFs激子行为和光催化机制的调控。