TY - JOUR
T1 - Emissive Ruthenium-Bisdiimine Complexes with Chelated Thioether Donors
AU - Wallenstein, Joachim
AU - Sundberg, Jonas
AU - McKenzie, Christine
AU - Abrahamsson, Maria
PY - 2016
Y1 - 2016
N2 - The photophysical properties of ruthenium(II) complexes of bidentate 2-[(alkylthio)methyl]pyridine (N,S) ligands have been systematically investigated. The co-ligands in the heteroleptic complexes were diimines (N,N ligands, e.g., bpy, phen) or tripodal tetradentate tris(2-pyridylmethyl)amine (tpa). Their X-ray structures revealed little variation in the Ru-S (2.31-2.33 Å) and Ru-N (2.06-2.11 Å) bond lengths. Despite this, considerable variation can be observed in the electrochemistry and spectroscopy measurements. The presence of the thioether sulfur donor results in a shift to a more positive potential of the Ru
2+/Ru
3+ process, and the absorption maxima are consequently blueshifted in [Ru(N,N)
2(N,S)]
2+ complexes compared with the [Ru(N,N)
3]
2+ analogues. The [Ru(N,N)
2(N,S)]
2+ complexes display strong room-temperature emission from
3MLCT states, governed by the N,N donors. This is corroborated by low-temperature steady-state emission studies, which revealed typical
3MLCT emission profiles and excited-state lifetimes of around 5-10 μs.
AB - The photophysical properties of ruthenium(II) complexes of bidentate 2-[(alkylthio)methyl]pyridine (N,S) ligands have been systematically investigated. The co-ligands in the heteroleptic complexes were diimines (N,N ligands, e.g., bpy, phen) or tripodal tetradentate tris(2-pyridylmethyl)amine (tpa). Their X-ray structures revealed little variation in the Ru-S (2.31-2.33 Å) and Ru-N (2.06-2.11 Å) bond lengths. Despite this, considerable variation can be observed in the electrochemistry and spectroscopy measurements. The presence of the thioether sulfur donor results in a shift to a more positive potential of the Ru
2+/Ru
3+ process, and the absorption maxima are consequently blueshifted in [Ru(N,N)
2(N,S)]
2+ complexes compared with the [Ru(N,N)
3]
2+ analogues. The [Ru(N,N)
2(N,S)]
2+ complexes display strong room-temperature emission from
3MLCT states, governed by the N,N donors. This is corroborated by low-temperature steady-state emission studies, which revealed typical
3MLCT emission profiles and excited-state lifetimes of around 5-10 μs.
KW - Electrochemistry
KW - N,S ligands
KW - Photophysics
KW - Ruthenium
KW - Synthetic methods
U2 - 10.1002/ejic.201501256
DO - 10.1002/ejic.201501256
M3 - Journal article
SN - 1434-1948
VL - 2016
SP - 897
EP - 906
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 6
ER -