title: Chiral bis(oxazoline) ruthenium complexes with bipyridyl-type N-heteroaromatics: comparative stereochemical and photochemical characterization of their Λ- and Δ-diastereomeric geminate isomers.
abstract: 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 1Λ and 1Δ, 4,4'-dimethyl-2,2'-bipyridyl (dmbpy) for 2Λ and 2Δ, and 1,10-phenanthroline (phen) for 3Λ and 3Δ), were separated as BF(4) and PF(6) salts and were subjected to the comparative studies of their stereochemical and photochemical characterization. DFT calculations of 1Λ and 1Δ 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+).
authors: Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, Nagasaki 852-8521, Japan. onishi@nagasaki-u.ac.jp
authors: Masayoshi
authors: M
authors: Onishi
authors: Yoko
authors: Y
authors: Tashiro
authors: Yasuhiro
authors: Y
authors: Arikawa
authors: Junko
authors: J
authors: Nagaoka
authors: Keisuke
authors: K
authors: Umakoshi
authors: Yusuke
authors: Y
authors: Sunada
authors: Koichi
authors: K
authors: Nozaki