LAUSR

We demonstrate a simple and generalizable method for the one pot, in situ formation of bimetallic metal–organic framework (MOF) materials decorated with crystallographically defined, low-valent metal sites. Solvothermal reactions between poly(carboxylated) aryl(phosphine) ligands and mixtures of higher- and lower-valent metal precursors achieves concomitant P–M complexation and MOF formation via metal–carboxylate network bonding. This method is demonstrated in the preparation of two new phosphine coordination materials, PCM-107 and PCM-74, which feature Ar3P–AuX (X = Cl, Br) and chelated PN–Cu2I2–PN units as the MOF building blocks, respectively. PCM-107 is an active catalyst for alkyne hydroaddition, while PCM-74 shows promise for the crystallization of MOFs bearing kinetically favored isomers.