Customizable metal-phenolic supraparticles based on rationally designed building blocks

Metal-phenolic networks (MPNs) as a versatile platform for particle engineering have been well developed due to their integrated benefits of both metal ions and phenolic molecules. However, the approaches to broaden their applications are limited due to the single-driving force from the coordination of these two components. Herein, we developed a universal approach to introducing programmable assembles into MPNs to form metal-phenolic supraparticles based on the rationally designed phenolic building blocks. These as-prepared building blocks can first assemble into primary nanoparticles driven by various controllable intermolecular interactions (i.e., metal-organic coordination, host-guest interaction, and hydrophobic interaction), followed by particle assembly with metal ions to coat on different templates. The introduction of multiple assembly modalities into phenolic building blocks enriches the functionalities of these metal-phenolic supraparticles, such as dual-pH responsibility, light-controllable permeability, and rapid fluorescence labeling of living cells. Our work provides a conceptual and practical paradigm for customizing MPNs with hierarchical structures by importing various assembly strategies via rationally designed phenolic building blocks.