A programmable organosulfate platform for concurrent molecular sequence and topology control

Abstract Metal–organic frameworks achieve structural complexity without deterministic sequence control. Conversely, biological macromolecules encode molecular information with extraordinary precision, yet provide limited access to discrete void-bearing topological complexity. Bridging these paradigms requires a programmable strategy capable of simultaneously defining molecular sequence and topology within a unified synthetic framework. Here we introduce a programmable platform that achieves this dual control. Iterative SuFEx-based homologation, coupled with controlled annulation, enables precise sequence definition and topological specification. Incorporation of a trifunctional scaffold permits access to bicyclic and cage-like molecular architectures with defined connectivities. Physicochemical analyses reveal that encoded sequence and topology dictate thermal stability and hydrodynamic behavior. Extension to polysulfate networks further demonstrates topology-dependent gelation, establishing programmable organosulfates as a versatile platform for constructing information-rich molecular systems and functional soft matter.