Luminescent cyanometallates based on phenylpyridine-Ir(III) units: solvatochromism, metallochromism, and energy-transfer in Ir/Ln and Ir/Re complexes

[Ir(ppy)(2)(CN)(2)](-) (ppy = anion of 2-phenylpyridine) and some substituted derivatives have been investigated for their ability to interact with additional metal cations, both in solution and the solid state, via the externally-directed cyanide lone pairs, and to act as energy-donors in the resulting assemblies. [Ir(ppy)(2)(CN)(2)](-) is slightly solvatochromic, showing a blue-shift of the lowest energy absorption manifold in water compared to organic solvents, and the solubilised Bu-t-substituted analogue [Ir((t)Buppy)(2)(CN)(2)](-) [(t)Buppy = anion of 2-(4-Bu-t-phenyl) pyridine] is also metallochromic with coordination of the cyanide lone pairs to two M(II) cations in MeCN (M = Ba, Zn) resulting in blue-shifts of the lowest-energy absorption and emission maxima. These effects are however modest because of (i) the presence of only two cyanide groups, and (ii) the fact that the lowest-energy excited state has a substantial (LC)-L-3 component and is therefore not purely charge-transfer in nature. Crystallisation of [Ir(ppy)(2)(CN)(2)](-) as its (PPN)(+) salt in the presence of excess of lanthanide(III) salts leads to formation of assemblies based on Ir-CN-Ln bonds, which generate in the solid state either Ir(2)Ln(2)(mu-CN) 4 square assemblies or linear trinuclear species with Ir-CN-Ln-NC-Ir cores. In the Ir2Eu2(mu-CN) 4 and Ir2Nd2(mu-CN)(4) complexes the Ir-based emission is substantially quenched due to energy-transfer to lower-lying f-f states of these lanthanide ions. In addition reaction of [Ir(F(2)ppy)(2)(CN)(2)](-) [F(2)ppy = cyclometallating anion of 2-(2,4-difluorophenyl) pyridine] with [Re(phen)(CO)(3)(MeCN)][PF6] in solution affords dinuclear IrRe and trinuclear IrRe2 species in which {Re(phen)(CO)(3)} units are attached to the N-donor termini of one or both of the cyanide groups; these complexes have been structurally characterised and display quantitative Ir -> Re energy-transfer, showing luminescence only from the Re(I) terminus on excitation of the Ir(III) unit.