title: Monodisperse oligofluorenes with keto defect as models to investigate the origin of green emission from polyfluorenes: synthesis, self-assembly, and photophysical properties.
abstract: Oligofluorenes (a trimer, pentamer, and heptamer) with one fluorenone unit in the center (OFnK: n=3, 5, or 7) were synthesized and used as models to understand the origin of the low-energy emission band in the photoluminescence and electroluminescence spectra of some polyfluorenes. All compounds form glasses with T(g) at 30 degrees C (OF3 K), 50 degrees C (OF5 K) and 57 degrees C (OF7 K). Oligomers OF5 K and OF7 K exhibit smectic liquid crystal phases that undergo transition to isotropic melts at 107 and 205 degrees C, respectively. Oligomer OF5 K could be obtained in form of single crystals. The X-ray structure analysis revealed the helical nature of the molecule and a helix reversal defect located at the central fluorenone unit. The packing pattern precludes formation of excimers. Electrochemical properties were investigated by cyclic voltammetry. The ionization potential (I(p)) and electron affinity (E(a)) were calculated from these data. Studies of the photophysical properties of OFnK in solution and thin film by steady-state and time-resolved fluorescence spectroscopic measurements suggest efficient funneling of excitation energy from the photoexcited fluorene segments to the low-energy fluorenone sites by both intra- and intermolecular hopping events whereby they give rise to green emission. Intermolecular energy transfer was investigated by using a model system composed of a highly defect free polyfluorene PF2/6 doped by OFnK. Förster-type energy transfer takes place from PF2/6 to OFnK. The energy-transfer efficiency increases predictably with increasing concentration of OFnK.
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Chunyan
authors.initials: C
authors.lastname: Chi
authors.forename: Chan
authors.initials: C
authors.lastname: Im
authors.forename: Volker
authors.initials: V
authors.lastname: Enkelmann
authors.forename: Andreas
authors.initials: A
authors.lastname: Ziegler
authors.forename: Günter
authors.initials: G
authors.lastname: Lieser
authors.forename: Gerhard
authors.initials: G
authors.lastname: Wegner