Programmable assembly of multiple donor-acceptor systems in metal-organic framework for heterogeneity manipulation and functions integration

•Macro- and micro-scale heterogeneity manipulation is realized in D-A-based MOFs •Programmable assembly of multiple D-A systems is achieved with MOF as platform •The heterostructure crystals of D-A MOF could be utilized as photoelectric devices 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. 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.