A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation

A base-resistant porphyrin metal–organic
framework (MOF),
namely PCN-602 has been constructed with 12-connected [Ni8(OH)4(H2O)2Pz12] (Pz
= pyrazolate) cluster and a newly designed pyrazolate-based porphyrin
ligand, 5,10,15,20-tetrakis­(4-(pyrazolate-4-yl)­phenyl)­porphyrin under
the guidance of the reticular synthesis strategy. Besides its robustness
in hydroxide solution, PCN-602 also shows excellent stability in aqueous
solutions of F–, CO32–, and PO43– ions. Interestingly, the
Mn3+-porphyrinic PCN-602, as a recyclable MOF catalyst,
presents high catalytic activity for the C–H bond halogenation
reaction in a basic system, significantly outperforming its homogeneous
counterpart. For the first time, a porphyrinic MOF was thus used as
an efficient catalyst in a basic solution with coordinating anions,
to the best of our knowledge.