Highly Efficient Cooperative Catalysis by CoIII(Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks

A series of porous twofold interpenetrated In‐CoIII(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In‐CoIII(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated CoIII(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis. Hand in hand: CoIII(porphyrin) pairs in an interpenetrating metal–organic frameworks work hand in hand to activate both substrates for highly efficient hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other, with a distance of about 8.8 Å, which is ideal for the simultaneous activation of both substrates of the reaction.