Metal-organic assemblies have received significant attention for catalytic and other applications, including gas and energy storage, due to their porosity and thermal/chemical stability. Here, we report the synthesis and physicochemical characterization of three metallosupramolecular assemblies consisting of isomeric ambidentate pyridyl-β-diketonate ligands L1–L3 and Cu(II) metal ions. It has been demonstrated that the topology and dimensionality of generated supramolecular aggregates depend on the location of the pyridine nitrogen donor atom in L1–L3. This is seen in characterization of two distinct 2D polymeric assemblies, i.e., [Cu(L1)₂]_n and [Cu(L2)₂]_n, in which both β-diketonate and pyridine groups are coordinated to the Cu(II) center, as well as in characterization of the mononuclear 1D complex Cu(L3)₂, in which the central atom is bound only by two β-diketonate units.

A series of switchable polymeric materials based on Ag(i), Pd(ii) and Pt(ii) and ambidentate ligand has been synthesized and showed enhanced catalytic activity in Heck reaction in comparison with their mononuclear counterparts.