Construction of Highly Proton-Conductive Zr(IV)-Based Metal–Organic Frameworks From Pyrrolo-pyrrole-Based Linkers with a Rhombic Shape

To date, numerous zirconium cluster-based metal–organic frameworks (Zr-MOFs) with attractive physical properties have been achieved thanks to tailorable organic linkers and versatile Zr clusters. Nevertheless, in comparison with the most-used high-symmetry organic linkers, low-symmetry linkers have rarely been exploited in the construction of Zr-MOFs. Despite challenges in predicting the structure and topology of the MOF, linker desymmetrization presents opportunities for the design of Zr-MOFs with unusual topologies and unexpected functionalities. Herein, we report for the first time the construction of two robust Zr-MOFs (IAM-7and IAM-8) from two pyrrolo-pyrrole-based low-symmetry tetracarboxylate linkers with a rare rhombic shape. The low symmetry of the linkers arises from the asymmetric pyrrolo-pyrrole core and the varying branch lengths, which play a critical role in the structural diversity between IAM-7and IAM-8seen from the structural analysis and lead to hydrophilic channels that contain uncoordinated carboxylate groups in the structure of IAM-7. Furthermore, the proton conductivity of IAM-7displays a high temperature and humidity dependence where the proton conductivity increases from 2.84 × 10–8S cm–1at 30 °C and 40% relative humidity (RH) to 1.42 × 10–2S cm–1at 90 °C and 95% RH, making it among one of the most conductive Zr-MOFs. This work not only enriches the library of Zr-MOFs but also offers a platform for the design of low-symmetry linkers toward the structural diversity or irregularity of MOFs as well as their structure-related properties.