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Linker conjugation effects in rhenium(I) bifunctional hole transport/emitter molecules

Journal Article


Abstract


  • Spectroscopic, electrochemical and density functional theory (DFT) methods have been employed to investigate a group of [Re(CO)3(HT)ACHTUNGTRENUNG(phen)]+ complexes (phen=1,10-phenanthroline), and in particular the level of electronic communication between various hole-transporting (HT) ligands and the rhenium centre. Here, the HT ligand consists of a coordinating pyridine connected to dimethylaniline group through a single-, double- or triple-bond-connecting system. Electronic absorption, resonance Raman, and steady-state emission spectroscopy combined with lifetime

    studies and DFT calculations suggest that multiple dp(Re)!p*ACHTUNGTRENUNG(phen) metal-to-ligand charge transfers (MLCTs) exist for each complex, two of which significantly absorb at about 340 and 385 nm, and one that emits at approximately 540 nm. In the complexes containing more-conjugated HT

    ligands, non-emissive intraligand transitions (IL(HT)) exist with energies between the ground and MLCT excited states. The overlap of these IL(HT) transitions and the absorbing MLCT of lowest energy deactivates emission resulting from about 385 nm excitation, and lowers the quantum yield and excited-

    state lifetimes of these complexes.

    Cyclic voltammetry experiments indicate that throughout the series investigated, the highest occupied molecular orbital (HOMO) of each complex is centred on the HT ligand, while the occupied molecular orbitals localised on the rhenium are lower in energy.

Authors


  •   Cleland, Deirdre M. (external author)
  •   Irwin, Garth (external author)
  •   Wagner, Pawel
  •   Officer, David L.
  •   Gordon, Keith C. (external author)

Publication Date


  • 2009

Citation


  • Cleland, D. M., Irwin, G., Wagner, P. W., Officer, D. L. & Gordon, K. C. (2009). Linker conjugation effects in rhenium(I) bifunctional hole transport/emitter molecules. Chemistry: A European Journal, 15 (15), 3682-3690.

Scopus Eid


  • 2-s2.0-63849108093

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/371

Number Of Pages


  • 8

Start Page


  • 3682

End Page


  • 3690

Volume


  • 15

Issue


  • 15

Place Of Publication


  • http://www.wiley-vch.de/home/chemistry

Abstract


  • Spectroscopic, electrochemical and density functional theory (DFT) methods have been employed to investigate a group of [Re(CO)3(HT)ACHTUNGTRENUNG(phen)]+ complexes (phen=1,10-phenanthroline), and in particular the level of electronic communication between various hole-transporting (HT) ligands and the rhenium centre. Here, the HT ligand consists of a coordinating pyridine connected to dimethylaniline group through a single-, double- or triple-bond-connecting system. Electronic absorption, resonance Raman, and steady-state emission spectroscopy combined with lifetime

    studies and DFT calculations suggest that multiple dp(Re)!p*ACHTUNGTRENUNG(phen) metal-to-ligand charge transfers (MLCTs) exist for each complex, two of which significantly absorb at about 340 and 385 nm, and one that emits at approximately 540 nm. In the complexes containing more-conjugated HT

    ligands, non-emissive intraligand transitions (IL(HT)) exist with energies between the ground and MLCT excited states. The overlap of these IL(HT) transitions and the absorbing MLCT of lowest energy deactivates emission resulting from about 385 nm excitation, and lowers the quantum yield and excited-

    state lifetimes of these complexes.

    Cyclic voltammetry experiments indicate that throughout the series investigated, the highest occupied molecular orbital (HOMO) of each complex is centred on the HT ligand, while the occupied molecular orbitals localised on the rhenium are lower in energy.

Authors


  •   Cleland, Deirdre M. (external author)
  •   Irwin, Garth (external author)
  •   Wagner, Pawel
  •   Officer, David L.
  •   Gordon, Keith C. (external author)

Publication Date


  • 2009

Citation


  • Cleland, D. M., Irwin, G., Wagner, P. W., Officer, D. L. & Gordon, K. C. (2009). Linker conjugation effects in rhenium(I) bifunctional hole transport/emitter molecules. Chemistry: A European Journal, 15 (15), 3682-3690.

Scopus Eid


  • 2-s2.0-63849108093

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/371

Number Of Pages


  • 8

Start Page


  • 3682

End Page


  • 3690

Volume


  • 15

Issue


  • 15

Place Of Publication


  • http://www.wiley-vch.de/home/chemistry