The rational design of metal-organic frameworks (MOFs) is one of the driving forces behind the great success that this class of materials is experiencing. The so-called isoreticular approach is a key design tool, very often used to tune the size, steric properties, and additional functional groups of the linker used. In this work, we go one step further and show that even linkers with two different coordinating groups, namely, phosphonate and phosphinate, can form isoreticular MOFs. This effectively bridges the gap between MOFs utilizing phosphinate and phosphonate coordinating groups. Using a novel bifunctional ligand, 4-[hydroxy(methyl)phosphoryl]phenylphosphonic acid [H3PPP(Me)], we were able to prepare ICR-12, a MOF isoreticular to already published MOFs containing bisphosphinate linkers (e.g., ICR-4). An isostructural MOF ICR-13 was also successfully prepared using 1,4-benzenediphosphonic acid. We envisage that this strategy can be used to further enlarge the pool of MOFs.

Department of Chemistry and Industrial Chemistry University of Pisa Via Giuseppe Moruzzi 13 Pisa 56124 Italy

Department of Structure Analysis Institute of Physics Czech Academy of Sciences Prague 18221 Czech Republic

Faculty of Science Charles University 128 00 Praha 2 Czech Republic

Institute of Advanced Materials Wrocław University of Science and Technology Wybrzeże Wyspiańskiego 27 Wrocław 50 370 Poland

Institute of Inorganic Chemistry of the Czech Academy of Sciences 250 68 Řež Czech Republic

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