Dramatic improvement of stability by in situ linker cyclization of a metal–organic framework

We employ a two-step strategy for accessing crystalline porous covalent networks of highly conjugated π-electron systems. For this, we first assembled a crystalline metal–organic framework (MOF) precursor based on Zr(IV) ions and a linear dicarboxyl linker molecule featuring backfolded, highly unsaturated alkyne backbones; massive thermocyclization of the organic linkers was then triggered to install highly conjugated, fused-aromatic bridges throughout the MOF scaffold while preserving the crystalline order. The formation of cyclized carbon links not only greatly strengthens the precursor coordination scaffold, but also, more importantly, enhances electroactivity and charge transport throughout the polycyclic aromatic grid.