Mesoscopic superstructures of flexible porous coordination polymers synthesized via coordination replication.

The coordination replication technique is employed for the direct conversion of a macro- and mesoporous Cu(OH)2-polyacrylamide composite to three-dimensional superstructures consisting of the flexible porous coordination polymers, Cu2(bdc)2(MeOH)2 and Cu2(bdc)2(bpy) (bdc2- = 1,4-benzenedicarboxylate, bpy = 4,4'-bipyridine). Detailed characterization of the replicated systems reveals that the structuralization plays an important role in determining the adsorptive properties of the replicated systems, and that the immobilization of the crystals within a higher-order architecture also affects its structural and dynamic properties. The polyacrylamide polymer is also found to be crucial for maintaining the structuralization of the monolithic systems, and in providing the mechanical robustness required for manual handling. In all, the results discussed here demonstrate a significant expansion in the scope of the coordination replication strategy, and further confirms its utility as a highly versatile platform for the preparation of functional three-dimensional superstructures of porous coordination polymers.