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

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.

Automated summary

This study reports a programmable assembly method for multiple donor-acceptor (D-A) systems in metal-organic frameworks (MOFs) to achieve heterogeneity manipulation and function integration. By utilizing strong D-A interactions, multiple D-A systems can be assembled in the framework and their assembly can be predicted and programmed based on minimum-energy thermodynamic principles. By this method, PAH-dependent domains can be programmatically integrated in a MOF to produce distinct heterostructures.