Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands

Journal Article · Wed Apr 29 00:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00035a014· OSTI ID:6915650

Richter, M M; Brewer, K J ^[1]

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1. Washington State Univ., Pullman (United States)

The synthesis, electrochemical, spectroscopic, and spectroelectrochemical properties of [(bpy)[sub 2]Os(BL)Ru(bpy)[sub 2]](PF[sub 6])[sub 4] (where BL = 2,3-bis(2[prime]-pyridyl)pyrazine (dpp), 2,3-bis(2[prime]-pyridyl)quinoxaline (dpq), and 2,3-bis(2[prime]-pyridyl)benzoquinoxaline (dpb) and bpy = 2,2[prime]-bipyridine) are reported. Addition of the Ru(bpy)[sub 2][sup 2+] moiety to the vacant coordination site on the bridging ligand in the [Os(bpy)[sub 2]BL][sup 2+] parent compounds resulting in a shift to lower energies of the metal-to-ligand charge transfer (MLCT) transitions terminating in the bridging-ligand-based [pi]* orbital as well as a shift to more positive potential of the bridging-ligand-based electrochemical reductions. The lowest energy electronic transition in these mixed-metal systems have been assigned to overlapping Os(d[pi]) [yields] BL([pi]*) and Ru(d[pi]) [yields] BL([pi]*) [sup 1]MLCT transitions with the OS(d[pi]) [yields] BL([pi]*) transition occurring at slightly lower energies. On the basis of spectroelectrochemical experiments, the first and second reductions of the bimetallic complexes have been assigned to sequential reductions of the bridging ligand.

• OSTI ID: 6915650
• Journal Information: Inorganic Chemistry; (United States), Vol. 31:9; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OSMIUM COMPLEXES
CHEMICAL PREPARATION
ELECTROCHEMISTRY
RUTHENIUM COMPLEXES
ABSORPTION SPECTRA
BIPYRIDINES
CHARGE TRANSPORT
ENERGY-LEVEL TRANSITIONS
LIGANDS
REDOX REACTIONS
REDUCTION
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
AZINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
HETEROCYCLIC COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
SPECTRA
SYNTHESIS
400201* - Chemical & Physicochemical Properties
400400 - Electrochemistry