From the same supramolecular framework to distinct types of porous liquids via in-situ transformation

Porous liquids (PLs), integrating porous hosts into flowing liquids through intermolecular interactions, attract significant attention, while their controlled synthesis remains challenging. Here we report a controllable in-situ transformation strategy to fabricate distinct types of PLs from the same supramolecular framework (SMF). Two isomorphic polyethylene-glycol-based ionic liquids, IL-Br and IL-NTf₂, differing only in anions, exhibit contrasting electrostatic interactions with the SMF. Strong attraction between IL-Br and the SMF disrupts the ionic bonds within the framework, yielding a type II PL, PL2(SMF-Br), while electrostatic repulsion in IL-NTf₂ preserves the framework, producing a type III PL, PL3(SMF-NTf₂). These tailored host-solvent interactions endow PL2(SMF-Br) with over twice the CO₂ uptake and photoresponsivity of its counterpart, as well as record-high CO₂ capacity among reported type II PLs. In this work, we establish a general strategy for tunable PL construction through electrostatically guided host-solvent design.