Alternative EE/EO Mn(II)–Azide Coordination Polymers: From Magnetic Diversity and Charge Transport to Catalytic Hydrosilylation of Biomass-Derived Carbonyls

One-dimensional (1D) coordination polymers offer rich chemical tunability and magnetic and semiconducting properties, making them promising for advanced magnetic, optoelectronic, and catalytic applications. Coordination polymers constructed from paramagnetic metal ions and diverse linkers can display both magnetic and semiconducting properties, while their potential to dissociate into smaller metal-ligand fragments enables the formation of catalytically active species. In this work, we synthesized two manganese(II)-azido coordination polymers <b>1</b> and <b>2</b> by reacting Mn(ClO₄)₂·6H₂O with tridentate NNS donor ligands in the presence of sodium azide. X-ray diffraction (XRD) analysis confirmed a 1D polymeric chain topology featuring alternating double end-on (EO) and double end-to-end (EE) azido bridges. Notably, compound <b>2</b> features the smallest EO-bridging angles and the shortest EO-azide-bridged Mn···Mn separations reported to date among Mn(II)-azide chains adopting this specific bridging motif. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and DLS analyses revealed a more ordered nanostructure in <b>2</b>. Magnetic studies revealed distinct behaviors, with <b>1</b> exhibiting overall antiferromagnetic interactions, while <b>2</b> displayed a ferromagnetic exchange. Charge transport measurements reveal a slightly enhanced hole mobility for <b>2</b>, attributed to its structural ordering. Furthermore, both the polymers also demonstrate efficient catalytic activity in hydrosilylation of biomass-derived carbonyl compounds, depolymerization leads to the active Mn-species, and the path involves Mn-hydride intermediate.