N,N′-dimethylethylenediammonium cation as a template for layered inorganic frameworks and beyond

The templating role of the N,N′ -dimethylethylenediammonium (dmedaH 2 ) 2+ cation in the synthesis of layered inorganic frameworks has been focused on transition metal hydroselenites and hydrophosphites. Under this work new compounds with the general formula (dmedaH 2 )[ M (HSeO 3 ) 2 X 2 ] ( M = Mn, Co, Cu, Cd; X = Cl, Br) and (dmedaH 2 )[Mn(H 2 PO 3 ) 2 Cl 2 ], which adopt layered structures with distinct hydrogen-bonded motifs, have been synthesized and characterized by single crystal X-ray analysis. The (dmedaH 2 ) 2+ cation exhibits a dual role: stabilizing targeted 2D architectures and directing the formation of side products, such as (dmedaH 2 )[Cd 2 Cl 4 (HSeO 3 ) 2 ]·2H 2 O and (dmedaH 2 )[Cu(SeO 2 Br)Br 3 ] (containing rare SeO 2 Br - anions). Topological analysis reveals the structural complexity and connectivity of these stuctures, highlighting the interplay between cation geometry and inorganic layers. The work underscores the templating potential of dmedaH 2 2+ in designing novel materials, while also demonstrating limitations imposed by steric and electronic factors. These findings advance the understanding of organic-inorganic hybrid systems and their structural diversity. • New layered compounds (dmedaH 2 )[ M (HSeO 3 ) 2 X 2 ] ( M = Mn, Co, Cu, Cd; X = Cl, Br) and (dmedaH 2 )[Mn(H 2 PO 3 ) 2 Cl 2 ] have been synthesized and characterized. • The templating role of the N,N′ -dimethylethylenediammonium (dmedaH 2 ) 2+ cation is discussed.