Group I cation templated formation of luminescent mono- and bis-substituted thionaphthol heterobimetallic complexes of Pr, Nd, Eu and Tb

Metathesis of lanthanide tris di-tert-butyl beta-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-OC10H4But (2)- 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)[LnL(2)(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.