Reticular Synthesis of a pcu-b Framework: Digital Reticular Chemistry for Anisotropic Modulation and Multicomponent Integration

Abstract

Introduction of “heterogeneity within order” in metal-organic frameworks (MOFs) commonly leads to the increase of structural complexity, posing the question of whether it is possible to spatially arrange multicomponent in a simple network. Here, we focused on the integration of quaternary components into a simple pcu-b (primitive cubic unit-biparticle) network using [Zn₄O]-core cluster and paddle-wheel secondary building units (SBUs) alongside organic linkers. We systematically explored a design space of over 180 candidate configurations, identifying an optimal structure that balances synthetic feasibility and functional potential. Experimental validation confirmed the successful synthesis of the predicted framework, named as MAC-5, which exhibits unique anisotropic modulation enabled by the controlled spatial arrangement of distinct Zn₄O(COO)₄(NN)₂ and paddle-wheel SBUs. Extending this approach, we synthesized a series of iso-reticular analogs, presenting the tailored multiple functions from different multicomponent frameworks. MAC-5’s hetero-SBU arrangement enhanced the thermal and chemical stabilities and enabled programmable metal doping that defy expectations in pcu-based systems. This work establishes a reticular chemistry approach to engineering functional complexity within simple network topologies, providing a blueprint for the rational design of multicomponent MOFs with tailored properties.