TY - JOUR
T1 - Chiral bis(oxazoline) ruthenium complexes with bipyridyl-type N-heteroaromatics
T2 - Comparative stereochemical and photochemical characterization of their ∇- And Δ-diastereomeric geminate isomers
AU - Onishi, Masayoshi
AU - Tashiro, Yoko
AU - Arikawa, Yasuhiro
AU - Nagaoka, Junko
AU - Umakoshi, Keisuke
AU - Sunada, Yusuke
AU - Nozaki, Koichi
PY - 2011/6/6
Y1 - 2011/6/6
N2 - Diastereomeric geminate pairs of chiral bis(2-oxazoline) ruthenium complexes with bipyridyl-type N-heteroaromatics, λ- and Δ-[Ru(L-L)2(iPr-biox)]2+ (iPr-biox=(4S,4′S)-4, 4′-diisopropyl-2,2′-bis(2-oxazoline); L-L=2,2′-bipyridyl (bpy) for 1 λ and 1 Δ, 4,4′-dimethyl-2,2′-bipyridyl (dmbpy) for 2 λ and 2 Δ, and 1,10-phenanthroline (phen) for 3 λ and 3 Δ), were separated as BF4 and PF6 salts and were subjected to the comparative studies of their stereochemical and photochemical characterization. DFT calculations of 1 λ and 1 Δ electronic configurations for the lowest triplet excited state revealed that their MO-149 (HOMO) and MO-150 (lower SOMO) characters are interchanged between them and that the phosphorescence-emissive states are an admixture of a Ru-to-biox charge-transfer state and an intraligand excited state within the iPr-biox. Furthermore, photoluminescence properties of the two λ,Δ- diastereomeric series are discussed with reference to [Ru(bpy)3] 2+.
AB - Diastereomeric geminate pairs of chiral bis(2-oxazoline) ruthenium complexes with bipyridyl-type N-heteroaromatics, λ- and Δ-[Ru(L-L)2(iPr-biox)]2+ (iPr-biox=(4S,4′S)-4, 4′-diisopropyl-2,2′-bis(2-oxazoline); L-L=2,2′-bipyridyl (bpy) for 1 λ and 1 Δ, 4,4′-dimethyl-2,2′-bipyridyl (dmbpy) for 2 λ and 2 Δ, and 1,10-phenanthroline (phen) for 3 λ and 3 Δ), were separated as BF4 and PF6 salts and were subjected to the comparative studies of their stereochemical and photochemical characterization. DFT calculations of 1 λ and 1 Δ electronic configurations for the lowest triplet excited state revealed that their MO-149 (HOMO) and MO-150 (lower SOMO) characters are interchanged between them and that the phosphorescence-emissive states are an admixture of a Ru-to-biox charge-transfer state and an intraligand excited state within the iPr-biox. Furthermore, photoluminescence properties of the two λ,Δ- diastereomeric series are discussed with reference to [Ru(bpy)3] 2+.
KW - bis(oxazoline)s
KW - chiral complexes
KW - density functional calculations
KW - photoluminescence
KW - ruthenium
UR - http://www.scopus.com/inward/record.url?scp=84962343733&partnerID=8YFLogxK
U2 - 10.1002/asia.201000738
DO - 10.1002/asia.201000738
M3 - 学術論文
C2 - 21433299
AN - SCOPUS:84962343733
SN - 1861-4728
VL - 6
SP - 1405
EP - 1415
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 6
ER -