Heterogeneity manipulation of metal-organic frameworks (MOFs) can be utilized to rationally integrate multiple components aiming at complex functions. However, the spontaneous nature of MOF assembly makes its heterogeneity tuning challenging. Herein, we report the programmable assembly of multiple donor-acceptor (D-A) systems in MOF for heterogeneity manipulation and functions integration. The strong D-A interactions between polycyclic aromatic hydrocarbon (PAH) donors and triazine acceptor in (PAH)_x@NKU-111 resulted in highly varied PAH-dependent system energies. The assembly of multiple D-A systems in the framework could be well predicted and programmed based on minimum-energy thermodynamic principles. Accordingly, the integration of PAH-dependent MOF domains could be programmed in a MOF at the macro- and micro-scale to produce distinct heterostructures. The heterostructure MOF crystals, featuring integrated domain-dependent emission and continuous domain interfaces, could be utilized as photonic transistor. The achievement in this work indicates the potential of this strategy for the fabrication of complex crystalline photoelectric devices.

金属有机框架（MOF）的异质性操作可用于合理整合针对复杂功能的多个组件。然而，MOF 组装的自发性使其异质性调整具有挑战性。在这里，我们报告了 MOF 中多个供体-受体 (DA) 系统的可编程组装，用于异质性操作和功能集成。(PAH) _x @NKU-111中多环芳烃 (PAH) 供体和三嗪受体之间的强 DA 相互作用导致高度变化的多环芳烃依赖性系统能量。可以根据最小能量热力学原理很好地预测和编程框架中多个 DA 系统的组装。因此，PAH 依赖性 MOF 结构域的整合可以在宏观和微观尺度的 MOF 中进行编程，以产生不同的异质结构。具有集成域相关发射和连续域界面的异质结构 MOF 晶体可用作光子晶体管。这项工作的成就表明了这种策略在制造复杂晶体光电器件方面的潜力。