Metathesis of lanthanide tris di-tert-butyl β-diketonates ([Ln(thd)3] Ln = Pr, Nd, Eu, Tb) with one or two equivalents of group 1 salts of the sulfur bridged binaphtholate dianion [1,1′-S(2-OC10H4But2-3,6) 2]2-, [M2L], M = K, Li affords luminescent mono- and bis-ligand substituted complexes ML[LnL(thd)2].L; M = K, Ln = Pr 1, Nd 2, Eu 3 and Tb 4 (L = thf, diethyl ether or toluene) and M(thf)2[LnL2(thd)]; M = Li, Ln = Pr 5, Nd 6, Eu 7, Tb 8. The potassium salt [K2L] affords mono-L substituted complexes most cleanly, while the lithium salt [Li2L] yields the bis-L substituted complexes most cleanly. The L ligands function as antenna for the sensitised lanthanide-centred emission in Eu3+ and Tb3+ complexes. The X-ray single-crystal structures of mono- and bis-L lanthanide complexes of Nd3+ are presented. © The Royal Society of Chemistry 2006.