Room-temperature phosphorescence (RTP) has drawn considerable attention due to its fascinating applications. Herein, we report the achievement of multistimulus responsive RTP by utilizing the customizable donor–acceptor (D–A) metal–organic framework (MOF) platform for charge-transfer (CT)-based triplet state tuning. A succession of electron-rich donors was introduced into the triazine-based electron-deficient framework ( NKU-Mg-2) to give D–A MOFs ( A1– A3) featuring CT-based emission. Notably, donors are designed and guided by heavy atom effect (–Br) to enhance the spin–orbit coupling, thereby achieving a fine-tuning excited state, resulting in the manipulation of phosphorescence from low temperature ( A1) to room temperature ( A2). Moreover, enhanced RTP intensity is further achieved by facilely altering the halogen functionalization ( A3). The modulated A3 simultaneously achieves multiple stimulus responses to X-ray, temperature, and oxygen, rendering it a promising candidate for novel optical sensors. This work not only achieves flexible control over the excited state but also presents a novel approach for developing multistimulus responsive intelligent optical materials.

室温磷光（RTP）因其令人着迷的应用而引起了广泛的关注。在此，我们报告了通过利用可定制的供体-受体（D-A）金属有机框架（MOF）平台进行基于电荷转移（CT）的三重态调节，实现了多刺激响应RTP。一系列富电子供体被引入到基于三嗪的缺电子框架中（ NKU-Mg-2) 得到 D–A MOF ( A1– A3）具有基于 CT 的发射。值得注意的是，供体是通过重原子效应（-Br）设计和引导的，以增强自旋轨道耦合，从而实现微调激发态，从而实现低温磷光的操控。 A1）至室温（ A2）。此外，通过轻松改变卤素官能化可以进一步实现增强的 RTP 强度（ A3）。调制的 A3同时实现对 X 射线、温度和氧气的多种刺激响应，使其成为新型光学传感器的有希望的候选者。这项工作不仅实现了对激发态的灵活控制，而且为开发多刺激响应智能光学材料提供了一种新方法。