Robust Supramolecular Nano?Tunnels Built from Molecular Bricks**

Herein we report a linear ionic molecule that assembles into supramolecular nano-tunnel structure through synergy of trident-type interactions and ?-? stacking interactions. The crystal exhibits anisotropic guest adsorption behavior. material shows good thermal stability undergoes multi-stage single-crystal-to-single-crystal phase transformations to nonporous on heating. remarkable chemical under both acidic basic conditions, which is rarely observed in organic frameworks often related structures with designed hydrogen-bonding Because the high polarity tunnels, this molecular also large CO2 -adsorption capacity while excluding other gases at ambient temperature, leading /CH4 selectivity. Aggregation-induced emission molecules gives bulk crystals vapochromic properties.