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Synthesis, characterization, and photophysics of oxadiazole- and diphenylaniline-substituted Re(I) and Cu(I) complexes

Journal Article


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Abstract


  • Transition-metal complexes of the types [Re(CO)3Cl(NN)], [Re(CO)3py(NN)]+, and [Cu(PPh3)2(NN)]+, where NN = 4,4′-bis(5-phenyl-1,3,4-oxadiazol-2-yl)-2,2′-bipyridine (OX) and 4,4′-bis(N,N-diphenyl-4-[ethen-1-yl]-aniline)-2,2′-bipyridine (DPA), have been synthesized and characterized. Crystal structures for [Re(CO)3Cl(DPA)] and [Cu(PPh3)2(OX)]BF4 are presented. The crystal structure of the rhenium complex shows a trans arrangement of the ethylene groups, in agreement with density functional theory calculations. The structure of the copper complex displays the planar aromatic nature of the bpy–oxadiazole ligand. Density functional theory modeling of the complexes was supported by comparison of calculated and experimental normalized Raman spectra; the mean absolute deviations of the complexes were <10 cm–1. The Franck–Condon state was investigated using UV–vis and resonance Raman spectroscopic as well as density functional theory computational techniques. It was shown that the lowest energy absorption peaks are metal to ligand charge transfer and ligand-centered charge transfer for the oxadiazole- and diphenylaniline-substituted bipyridine ligands, respectively. The lowest energy excited states were characterized using transient emission and absorption spectroscopic techniques in conjunction with density functional theory calculations. These showed that the DPA complexes had ligand-centered nonemissive “dark” states with lifetimes ranging from 300 to 2000 ns.

Authors


  •   Horvath, Raphael (external author)
  •   Fraser, Michael (external author)
  •   Cameron, Scott A. (external author)
  •   Blackman, Allan G. (external author)
  •   Wagner, Pawel
  •   Officer, David L.
  •   Gordon, Keith C. (external author)

Publication Date


  • 2013

Citation


  • Horvath, R., Fraser, M. G., Cameron, S. A., Blackman, A. G., Wagner, P., Officer, D. L. & Gordon, K. C. (2013). Synthesis, characterization, and photophysics of oxadiazole- and diphenylaniline-substituted Re(I) and Cu(I) complexes. Inorganic Chemistry: including bioinorganic chemistry, 52 (3), 1304-1317.

Scopus Eid


  • 2-s2.0-84873364002

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1142&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/143

Number Of Pages


  • 13

Start Page


  • 1304

End Page


  • 1317

Volume


  • 52

Issue


  • 3

Abstract


  • Transition-metal complexes of the types [Re(CO)3Cl(NN)], [Re(CO)3py(NN)]+, and [Cu(PPh3)2(NN)]+, where NN = 4,4′-bis(5-phenyl-1,3,4-oxadiazol-2-yl)-2,2′-bipyridine (OX) and 4,4′-bis(N,N-diphenyl-4-[ethen-1-yl]-aniline)-2,2′-bipyridine (DPA), have been synthesized and characterized. Crystal structures for [Re(CO)3Cl(DPA)] and [Cu(PPh3)2(OX)]BF4 are presented. The crystal structure of the rhenium complex shows a trans arrangement of the ethylene groups, in agreement with density functional theory calculations. The structure of the copper complex displays the planar aromatic nature of the bpy–oxadiazole ligand. Density functional theory modeling of the complexes was supported by comparison of calculated and experimental normalized Raman spectra; the mean absolute deviations of the complexes were <10 cm–1. The Franck–Condon state was investigated using UV–vis and resonance Raman spectroscopic as well as density functional theory computational techniques. It was shown that the lowest energy absorption peaks are metal to ligand charge transfer and ligand-centered charge transfer for the oxadiazole- and diphenylaniline-substituted bipyridine ligands, respectively. The lowest energy excited states were characterized using transient emission and absorption spectroscopic techniques in conjunction with density functional theory calculations. These showed that the DPA complexes had ligand-centered nonemissive “dark” states with lifetimes ranging from 300 to 2000 ns.

Authors


  •   Horvath, Raphael (external author)
  •   Fraser, Michael (external author)
  •   Cameron, Scott A. (external author)
  •   Blackman, Allan G. (external author)
  •   Wagner, Pawel
  •   Officer, David L.
  •   Gordon, Keith C. (external author)

Publication Date


  • 2013

Citation


  • Horvath, R., Fraser, M. G., Cameron, S. A., Blackman, A. G., Wagner, P., Officer, D. L. & Gordon, K. C. (2013). Synthesis, characterization, and photophysics of oxadiazole- and diphenylaniline-substituted Re(I) and Cu(I) complexes. Inorganic Chemistry: including bioinorganic chemistry, 52 (3), 1304-1317.

Scopus Eid


  • 2-s2.0-84873364002

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1142&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/143

Number Of Pages


  • 13

Start Page


  • 1304

End Page


  • 1317

Volume


  • 52

Issue


  • 3