Complexes of ruthenium(II) with bpmRe(CO) sub 3 Cl and HAT(Re(CO) sub 3 Cl) sub 2 as ligands: Syntheses and redox and luminescence properties

Journal Article · Wed Mar 22 00:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00305a008· OSTI ID:5145908

Sahai, R; Rillema, D P; Shaver, R; Van Wallendael, S; Jackman, D C; Boldaji, M ^[1]

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1. Univ. of North Carolina, Charlotte (USA)

A series of mixed-metal complexes containing ruthenium and rhenium are reported. The new complexes are ((bpy)Ru-(bpmRe(CO){sub 3}Cl){sub 2})(PF{sub 6}){sub 2}, ((bpy){sub 2}RuHAT(Re(CO){sub 3}Cl){sub 2})(PF{sub 6}){sub 2}, and (Ru(bpmRe(CO){sub 3}Cl){sub 3})(PF{sub 6}){sub 2}. Optical transitions in the visible-uv spectrum are dominated by the presence of the ruthenium heterocycles that have absorption coefficients for the low-energy transition 1 order of magnitude greater than that of the rhenium chromophore. The low-energy transition blue-shifts in the series ((bpy){sub 2}Ru(bpmRe(CO){sub 3}Cl)){sup 2+} (558 nm) < ((bpy)Ru(bpmRe(CO){sub 3}Cl){sub 2}){sup 2+} (531 nm) < (Ru(bpmRe(CO){sub 3}Cl){sub 3}){sup 2+} (501 nm). Polarographic half-wave potentials of the metal-centered oxidations and the bridging-ligand reductions shift positively as the number of Re(CO){sub 3}Cl units increase. The E{sub {1/2}} values for the ((bpy){sub n}Ru(bpmRe(CO){sub 3}Cl){sub 3-n}){sup 2+/+} couple in the series with n = 0-2 were -0.1, -0.33, and -0.41 V vs SSCE, respectively. Two complexes ((bpy)Ru(bpmRe(CO){sub 3}Cl){sub 2}){sup 2+} and ((Ru-(bpmRe(CO){sub 3}Cl){sub 3})){sup 2+}, were found to luminesce weakly at room temperature in acetonitrile with lifetimes of 942 and 847 ns, respectively. In many respects, the mixed-metal complexes are shown to behave as if the bpmRe(CO){sub 3}Cl and HAT(Re(CO){sub 3}Cl){sub 2} chromophores are ligands coordinated to ruthenium(II). 17 refs., 8 figs., 4 tabs.

• DOE Contract Number: FG05-84ER13263
• OSTI ID: 5145908
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:6; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
SYNTHESIS
CHLORINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS FLUORIDES
RHENIUM COMPLEXES
RUTHENIUM COMPLEXES
EXPERIMENTAL DATA
LUMINESCENCE
REDOX REACTIONS
CHEMICAL REACTIONS
COMPLEXES
DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical &amp; Physicochemical Properties