Controlling the Packing of Metal–Organic Layers by Inclusion of Polymer Guests

The preparation of metal-organic structures with a controlled degree of disorder is currently one of the most promising fields of materials science. Here, we describe the effect of guest polymer chains on the transformation of a metal-organic framework (MOF). Heating a pillared MOF at a controlled temperature resulted in the exclusive removal of the pillar ligands, while the connectivity of the metal-organic square-grid layers was maintained. In the absence of a polymer, 2D-layers rearranged to form a new crystalline phase. In contrast, the presence of a polymer in the MOF inhibited totally the recrystallization, leading to a turbostratic phase with layers threaded and maintained apart by the polymer chains. This work demonstrates a new synthetic approach toward the preparation of anisotropic metal-organic materials with controlled disorder. It also reveals how guests can dramatically modify the conversion of host MOFs, even though no chemical reaction occurs between them.