Selective CO₂ Capture and High Proton Conductivity of a Functional Star‐of‐David Catenane Metal–Organic Framework

Network structures based on Star-of-David catenanes with multiple superior functionalities have been so far elusive, although numerous topologically interesting networks are synthesized. Here, a metal-organic framework featuring fused Star-of-David catenanes is reported. Two triangular metallacycles with opposite handedness are triply intertwined forming a Star-of-David catenane. Each catenane fuses with its six neighbors to generate a porous twofold intercatenated gyroid framework. The compound possesses exceptional stability and exhibits multiple functionalities including highly selective CO₂ capture, high proton conductivity, and coexistence of slow magnetic relaxation and long-range ordering.