Bimetallic Pt(II)-bipyridyl-diacetylide/Ln(III) tris-diketonate adducts based on a combination of coordinate bonding and hydrogen bonding between the metal fragments: syntheses, structures and photophysical properties

The luminescent Pt(II) complex [Pt(4,4'-Bu-t(2)-bipy){CC-(5-pyrimidinyl)}(2)] (1) was prepared by coupling of [Pt(4,4'-Bu-t(2)-bipy)Cl-2] with 5-ethynyl-pyrimidine, and contains two pyrimidinyl units pendant from a Pt(H) bipyridyl diacetylide core; it shows luminescence at 520 nm which is typical of Pt(II) luminophores of this type. Reaction with [Ln(hfac)(3)(H2O)(2)] (hfac = anion of hexafluoroacetylacetone) affords as crystalline solids the compounds [1 center dot {Ln(hfac)(3)(H2O)}{Ln(hfac)(3)(H2O)(2)}] (Ln = Nd, Gd, Er, Yb), in which the {Ln(hfac)(3)(H2O)} unit is coordinated to one pyrimidine ring via an N atom, whereas the {Ln(hfac)(3)(H2O)(2)} unit is associated with two N atoms, one from each pyrimidine ring of 1, via N center dot center dot center dot HOH hydrogen-bonding interactions involving the coordinated water ligands on the lanthanide centre. Solution spectroscopic studies show that the luminescence of 1 is partly quenched on addition of [Ln(hfac)(3)(H2O)(2)] (Ln = Er, Nd) by formation of Pt(II)/Ln(III) adducts in which Pt(II)-> Ln(III) photoinduced energy-transfer occurs to the low-lying f-f levels of the Ln(Ill) centre. Significant quenching occurs with both Er(Ill) and Nd(III) because both have several f-f states which match well the (MLCT)-M-3 emission energy of 1. Time-resolved luminescence studies show that Pt(II)-Er(III) energy-transfer (7.0 x 10(7) M-1) is around three times faster than Pt(II)-> Nd(III) energy-transfer (approximate to 2 x 10(7) M-1) over the same distance because the luminescence spectrum of l overlaps better with the absorption spectrum of Er(111) than with Nd(III). In contrast Yb(111) causes no significant quenching of 1 because it has only a single f-f excited level which is a poor energy match for the Pt(II)-based excited state.