Synthesis, Structure, and Properties of Coordination Polymers with Layered Transition‐Metal Thiocyanato Networks

Reaction of 4‐ tert ‐butylpyridine ( t BP) with transition‐metal thiocyanates leads to the formation of compounds of composition [M(NCS) 2 ( t BP) 4 ] [M = Mn ( 1‐Mn ), Fe ( 1‐Fe ), Co ( 1‐Co ), Ni ( 1‐Ni )] that consist of discrete complexes, in which the metal centers are octahedrally coordinated by two terminal thiocyanato anions and four t BP ligands. If less t BP is used in the synthesis, two compounds of composition [M(NCS) 2 ( t BP) 2 ] n with M = Co ( 2‐Co ) and Ni ( 2‐Ni ) are obtained, in which the metal centers are linked into a 2D network by single thiocyanato anions. Thermal decomposition of 1‐Co leads to the formation of an additional modification of [Co(NCS) 2 ( t BP) 2 ] ( 3‐Co ). Magnetic measurements of 2‐Ni and 2‐Co reveal that 2‐Ni shows a ferromagnetic phase transition at T c = (14.8 ± 0.1) K and 2‐Co shows a transition to the magnetic state with uncompensated magnetic moment at (3.15 ± 0.03) K.