title: Efficient intramolecular charge transfer in oligoyne-linked donor-pi-acceptor molecules.
abstract: Studies are reported on a series of triphenylamine-(C[triple bond]C)(n)-2,5-diphenyl-1,3,4-oxadiazole dyad molecules (n=1-4, 1, 2, 3 and 4, respectively) and the related triphenylamine-C(6)H(4)-(C[triple bond]C)(3)-oxadiazole dyad 5. The oligoyne-linked D-pi-A (D=electron donor, A=electron acceptor) dyad systems have been synthesised by palladium-catalysed cross-coupling of terminal alkynyl and butadiynyl synthons with the corresponding bromoalkynyl moieties. Cyclic voltammetric studies reveal a reduction in the HOMO-LUMO gap in the series of compounds 1-4 as the oligoyne chain length increases, which is consistent with extended conjugation through the elongated bridges. Photophysical studies provide new insights into conjugative effects in oligoyne molecular wires. In non-polar solvents the emission from these dyad systems has two different origins: a locally excited (LE) state, which is responsible for a pi*-->pi fluorescence, and an intramolecular charge transfer (ICT) state, which produces charge-transfer emission. In polar solvents the LE state emission vanishes and only ICT emission is observed. This emission displays strong solvatochromism and analysis according to the Lippert-Mataga-Oshika formalism shows significant ICT for all the luminescent compounds with high efficiency even for the longer more conjugated systems. The excited-state properties of the dyads in non-polar solvents vary with the extent of conjugation. For more conjugated systems a fast non-radiative route dominates the excited-state decay and follows the Engelman-Jortner energy gap law. The data suggest that the non-radiative decay is driven by the weak coupling limit.
authors.affiliation: Department of Chemistry, Durham University, Durham DH1 3LE, UK. lars-olof.palsson@durham.ac.uk
authors.forename: Lars-Olof
authors.initials: LO
authors.lastname: Pålsson
authors.forename: Changsheng
authors.initials: C
authors.lastname: Wang
authors.forename: Andrei S
authors.initials: AS
authors.lastname: Batsanov
authors.forename: Simon M
authors.initials: SM
authors.lastname: King
authors.forename: Andrew
authors.initials: A
authors.lastname: Beeby
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Monkman
authors.forename: Martin R
authors.initials: MR
authors.lastname: Bryce
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D005453:Fluorescence; D008958:Models, Molecular; D015394:Molecular Structure; D010069:Oxadiazoles / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000480:Alkynes; D010069:Oxadiazoles; D010165:Palladium