Metal–organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactionsof DNA, 11 distinct MOF particle–inorganic particle core–satelliteclusters were synthesized. In these hybrid nanoclusters, the relativestoichiometry, size, shape, and composition of the building blockscan all be independently controlled. This work provides access toa new set of nucleic acid–nanoparticle conjugates, which maybe useful as programmable material building blocks and as probes formeasuring and manipulating intracellular processes.
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