Linkage Position-Controlled Synthesis of Diverse Zirconium Metal-Organic Frameworks with Prominent Intrinsic Proton Conductivities.

Herein, by engineering the geometries of the organic linkers, two pyrrolo-pyrrole-based low-symmetry tetracarboxylate linkers (TAPPs) were successfully designed and subsequently used for the construction of two new zirconium-based metal-organic frameworks (Zr-MOFs) ( and ). The reduction of the linker symmetry arises from both the asymmetric pyrrolo-pyrrole core and the integration of both the - and -benzoate coordination groups on the linkers. Both MOFs are composed of 8-connected Zr nodes and 4-connected highly deformed TAPP linkers with the same topology, but distinct linker arrangements can be observed in two structures.