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

Abstract 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 CO 2 capture, high proton conductivity, and coexistence of slow magnetic relaxation and long‐range ordering.