The self-assembly of molecules into large supramolecular structures is an important feature in biology and is now readily achieved in inorganic coordination chemistry with appropriate helicating ligands and metal ions. Work in our laboratory has shown that (S,S)-tetraphos spontaneously self-assembles dinuclear metal helicates of the type of (M)-[M2{(R,R)-tetraphos}2](PF6)2 upon reaction with univalent silver and gold salts and (M)-[Pt2{(R,R)-tetraphos}2](OTf)4 upon reaction with Pt(COD)Cl2 in the presence of TMSOTf. The central 10-membered ring in each of these complexes has a chiral twist-boat-chair-boat conformation; the δ or λ twist of the ring generates a parallel or double α-helix conformer of the helicate. Current work is focused on the synthesis of similar complexes involving zero-valent metals and the synthesis of tetraphosphines with substituted backbones that will stabilise the double ?-helix conformer of the helicate over that of the parallel helix conformer.