2 , 4 - Triphospholyl anions – versatile building blocks for the formation of 1 D , 2 D and 3 D assemblies † ‡

The potential of K[P3C2R2] (R = Bu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(I) halides resulted in the formation of a large variety of unprecedented one-, twoand even three-dimensional aggregates. The 3D networks showed an interesting topological similarity to allotropes of carbon: diamond and the theoretically proposed polybenzene. Furthermore, the negative charge of the phospholyl ligand favoured the generation of cationic CuaXb (a > b, X = Cl, Br, I) assemblies, a challenging area within the well-studied coordination chemistry of CuX units. In addition, the 1D strands were also characterized in solution, revealing the presence of oligomeric units.