Trends in metal–ligand orbital mixing in generic series of ruthenium N-donor ligand complexes—effect on electronic spectra and redox properties

✍ Scribed by S.I Gorelsky; E.S Dodsworth; A.B.P Lever; A.A Vlcek

• Publisher: Elsevier Science
• Year: 1998
• Tongue: English
• Weight: 489 KB
• Volume: 174
• Category: Article
• ISSN: 0010-8545
• DOI: 10.1016/s0010-8545(98)00144-1

✦ Synopsis

Generic series of complexes [Ru(bpy) 3-n (LL) n ]2+ (bpy=2,2∞-bipyridine), where LL is a diimine ligand including specifically 2,2∞-bipyrazine (bpz), 2,2∞-azobipyridine (abpy), and obenzoquinonediimine (bqdi), are studied with respect to their electrochemistry, optical spectroscopy and electronic structure as elucidated using Zerner's INDO/S method. Characteristics of their electrochemistry and optical spectroscopy are explained in terms of mixing between ruthenium d orbitals and diimine ligand p and p* orbitals, increasing in importance from bpy to bpz to abpy to bqdi. In this last case, these species have characteristics not unlike fully delocalized organic molecules.