Conductive metal-organic frameworks (MOFs) have a wide range of applications in supercapacitors, electrocatalysts, and fuel cells, while gas-driven conductive MOFs have not yet been synthesized so far. Herein, we report a gas-driven conductive MOF () constructed from calix[4]resorcinarene macrocycle and Co(II) cations, which shows the conductivity enhancement by about eight orders of magnitude through NO adsorption. The conductivities of MOF before and after the adsorption of NO were calculated to be about 1.3 × 10 and 8.4 × 10 S/cm, respectively. MOF realizes the conversion from an insulator to a conductor by adsorbing NO. When NO is evacuated, MOF quickly changes from a conductor back to an insulator in 42 s. In the crystal structure of NO-adsorbed MOF (termed as ), NO molecule connects Co(II) and uncoordinated carboxylate groups through hydrogen-bonding interactions to form a conductive pathway, greatly reducing the electron transmission distance between each two metal clusters. In addition, NO molecule and HO may also form a conductive pathway by hydrogen-bonding interactions. This work presents an interesting macrocycle-based MOF with a NO-driven on/off conductivity switch, proving the possibility for designing advanced gas-driven conductive systems.
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