We describe the concept of increasing the nuclearity of a previously reported high-spin Cu5Gd2 core using a fine-tuning ligand approach. Thus, two Cu(9)Ln(2) coordination clusters, with Ln = Dy (1) and Gd (2), were synthesized with the Gd compound having a ground spin state of 17/2 and the Dy analogue showing single-molecule-magnet behavior in zero field.