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

Abstract

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.

Authors:
;  [1]
  1. Washington State Univ., Pullman (United States)
Publication Date:
OSTI Identifier:
6915650
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 31:9; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Richter, M M, and Brewer, K J. Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands. United States: N. p., 1992. Web. doi:10.1021/ic00035a014.
Richter, M M, & Brewer, K J. Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands. United States. doi:10.1021/ic00035a014.
Richter, M M, and Brewer, K J. Wed . "Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands". United States. doi:10.1021/ic00035a014.
@article{osti_6915650,
title = {Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands},
author = {Richter, M M and Brewer, K J},
abstractNote = {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.},
doi = {10.1021/ic00035a014},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 31:9,
place = {United States},
year = {1992},
month = {4}
}