Topological motifs in dicyanamides of transition metals

Abstract

Dicyanamides of d-metals provide a wide range of magnetic properties tuned by external cations, encapsulated ions, and coordination modes of anions. Analysis of molecular, one-periodic (1D chain), two-periodic (2D layered), and three-periodic (3D framework) networks formed by transition metals in their dicyanamides was carried out. All dicyanamides were treated as systems of nodes (metal centers and polytopic ligands) and spacers (bridge dicyanamide anions and co-ligands). The most typical coordination numbers, the role of the dicyanamide, and the effect of terminal and chelate co-ligands on the dimensionality and type of overall architecture were described. A knowledge-based system to predict possible architectures of novel dicyanamides was described and tested on samples of five complexes. The synthesis and spectroscopic and structural properties of the synthesized compounds were described. It was demonstrated that the novel compounds realize square lattice (sql), honeycomb (hcb) or simple chain (2C1) motifs, which were estimated to be the 1st and the 2nd of the most abundant topologies for 2D networks and the most expected 1D motif, respectively.