A programmable organosulfate platform for concurrent molecular sequence and topology control.

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.