Three new complexes [Ni(β-dkt)2(NH2-quin)] {β-dkt=2,2,6,6-tetramethylheptane-3,3-dionate (tmhd) 1, hexafluoroacetylacetonate (hfac) 2, 1,3-diphenylpropanedionate (dbm) 3} have been prepared by reacting [Ni(β-dkt)2(H2O)2] with 8-aminoquinoline (NH2-quin). [Ni(tmhd)2(NH2-quin)] is found to be solvatochromic exhibiting a square planar geometry in CH2Cl2, acetone, and acetonitrile with the tmhd ligand acting unusually as a counteranion while in THF and DMSO the complex is octahedral. In contrast, 2 and 3 are octahedral in all solvents. Single crystal X-ray diffraction studies reveal octahedral nickel centres with a cis arrangement of the β-diketonates. The molecular packing consists of hydrogen bonded dimers which in the case of 2 and 3 are connected to one another via π···π and C–H⋯π interactions, respectively. Cyclic voltammetry shows 1 and 3 oxidise irreversibly at 0.46 and 1.17V, respectively.