Luminescent lanthanide complexes have been prepared by exploiting the interaction between lanthanide DO3A complexes and chromophore bearing carboxylates or phosphonates. This interaction can be utilised to probe the choice of sensitising chromophore suited to a given lanthanide. Furthermore, ternary complexes obtained from chromophore appended carboxylates dissociate in the presence of phosphate, while those obtained from phosphonates do not.
Tetrathiafulvalene carboxylate associates with the charge neutral complex, Yb.DO3A, in methanolic solution to give rise to a novel ternary species; the tetrathiafulvalene unit transfers energy to the lanthanide, causing luminescence from the Yb metal, indicating for the first time that an electron donor chromophore can act as an efficient sensitiser in a self-assembled system containing a lanthanide acceptor.
A series of symmetrical 1,3-dithiole-2-thiones and -ones have been prepared via double lithiation of vinylene trithiocarbonate followed by trapping of the dianions with aryl carbaldehydes. The resulting diols are oxidised in high yield and the corresponding diketones are converted to thiophenes and furans using P2S5-NaHCO3 and P(OEt)(3), respectively. The majority of triaryl compounds undergo two reversible oxidation processes in the range 10.86 to 11.57 V (vs. Ag/AgCl). The charge-transfer complex (8c)(2).TCNQ forms mixed donor-acceptor stacks. EPR spectroscopy confirms the presence of an open shell species, but the material is an electrical insulator. Reaction of 8c with diiodine forms a charge transfer complex with a conductivity of 1.2x10(-4) S cm(-1)
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