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Spectroelectrochemical properties of ruthenium(II) tris chelate complexes 2,2'-bipyrimidine and 2,2'-bipyrazine

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00264a007· OSTI ID:5522182
The electronic absorption and resonance Raman (RR) spectra of the reduction products of (Ru(bpm)/sub 3/)/sup 2-n/ and mixed-ligand complexes (Ru(bpz)/sub x/(bpy)/sub 3-x/)/sup 2-n/ (x = 1-3, n = 0-3) are discussed, as well as the low-temperature electron spin resonance (ESR) spectrum of (Ru(bpz)/sub 3/)/sup 0/ (bpm = 2.2'-bipyrimidine, bpz = 2,2'-bipyrazine, and bpy = 2,2'-bipyridine). The ultraviolet (UV) absorption and RR spectra for the reduction products of the tris(bipyrimidine) complex are analogous to those of the tris(bipyridine) complex and argue strongly for a localized redox orbital description. While the ESR and near-IR (near infrared) absorption spectra also argue for localized redox orbitals in the bpz complexes, the simple (bpz)/sub 3-n//(bpz/sup -/)/sub n/ ..pi.. ..-->.. ..pi..* chromophoric behavior typical in the UV absorption spectrum is not observed. Furthermore, there is a gradual shifting of the RR peaks as electrons are added, with no distinct vibrational pattern from reduced and unreduced bipyrazine ligands for the one- and two-electron-reduction products as seen in the complexes of (Ru(bpy)/sub 3/)/sup 2-n/ and (Ru(bpm)/sub 3/)/sup 2-n/.
Research Organization:
North Carolina State Univ., Raleigh
OSTI ID:
5522182
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:17; ISSN INOCA
Country of Publication:
United States
Language:
English