Structural characterization and spectroscopic studies of the (2-acetyl-6-(1-TEMPO-imino)ethyl)pyridine (pat) and the 2,6-bis(1-TEMPO-imino)ethyl)pyridine (pbtMe) ligands are presented. Their electrochemical properties are also discussed. Two new nickel complexes, [NiII(dip)(CH3CN)(H2O)2](BF4)2 (1) (dip = 2,6-(di-iminepyridine)) and [NiII(pbtMe)(CH3CN)3](BF4)2 (2) have been characterized by X-ray diffraction. The reaction of 1 with the tetraethyl ammonium pentacyanopropenide salt (Et4N)(pcp) affords the new compound [NiII(pcp)(dip)(CH3CN)](pcp) (3) for which X-ray diffraction studies evidence an usual bridging μ2 coordination mode for the pentacyanopropenide anion, leading to chains running along the [1 0 0] direction with Ni⋯Ni intra-chains distances of 10.653 Å. Magnetic measurements for 3 indicate that it presents antiferromagnetic interactions that can be reproduced with a S = 1 regular chain model with g = 2.115(1) and Jchain = −0.589(5) cm−1.