A bifunctional ligand 4,4-dimethyl-1-(pyridin-4-yl)pentane-1,3-dione (HL) able to provide two distinct coordination sites, i.e. anionic β-diketonate (after deprotonation) and neutral pyridine, has been used in the synthesis of Ag(I), Pd(II) and Pt(II) complexes that then have been applied as metalloligands for the construction of new heterometallic polymeric materials. The ambidentate nature of L- enables switching between different modes of coordination within mononuclear complexes or their conversion into polymeric species in a fully controllable way. The coordination-driven processes can be triggered by various stimuli, i.e. a metal salt addition or acid-base equilibria, and presents an efficient strategy for the generation of metallosupramolecular materials. As a consequence of self-assembly, new multimetallic coordination aggregates have been synthesized and characterized in depth in solution (1H NMR, ESI-MS) as well as in the solid state (XPS, SEM-EDS, FTIR, pXRD, TGA). Furthermore, the Pd-based assemblies have been found to be efficient catalyst precursors in the Heck cross-coupling reaction, demonstrating a direct impact of compositional and morphological differences on their catalytic activity.