[Cu(NH2CH2CH2NEt2){B6O7(OH)6}].5H2O (1) and [Cu(NH3)2{B6O7(OH)6}].2H2O (2) have been obtained as crystalline materials from aqueous solutions of Dynamic Combinatorial Libraries (DCLs) originating from B(OH)3 and appropriate Cu(II) amine complexes. These two Cu/O/B clusters are formed through self-assembly processes and contain tridentate hexaborate(2-)-3O ligands. Both compounds have been characterized by TGA/DSC, magnetic susceptibility measurements, IR spectroscopy, and single-crystal XRD studies. The intermolecular H-bond interactions between neighbouring hexaborate units are implicated in their templated synthesis. Compound 2 is a coordination polymer and stabilization is also gained through formation of an additional O-Cu coordinate bond. Steric congestion in 1 blocks formation of this bond resulting in insular complexes.