Structure and redox and photophysical properties of a series of ruthenium heterocycles based on the ligand 2,3-bis(2-pyridyl)quinoxaline
The synthesis, structure, and redox and photophysical properties of (Ru(bpy)/sub n/(BL)/sub 3-n/)/sup 2 +/, where n = 0-2, bpy is 2,2'-bipyridine, and BL is 2,3-bis(2-pyridyl)quinoxaline, are described. The (Ru(bpy)/sub 2/(BL))(PF/sub 6/)/sub 2/ complex crystallized in the monoclinic space group P2/sub 1//a and the cell parameters are repeated. All non-H atoms were refined anisotropically to an R value of 0.0672 for 5766 reflections with I > sigma(I). The ruthenium to nitrogen bond distances were Ru-N(pyridine) = 2.06 A (average) and Ru-N(pyrazine) = 2.096 (4) A. Absorption spectra contained bands (250-300 nm) in the ultraviolet region that were assignable to ligand ..pi.. ..-->.. ..pi..* transitions and visible bands (517-300 nm) that were assignable to d..pi.. ..-->.. ..pi..* MLCT transitions. Reduction potentials for the Ru/sup 3+/2+/ couples varied from about 1.40 to 1.70 V vs SSCE. Three reductions were observed and assigned to the one-electron reduction of each bidentate ligand. Weak luminescence was observed, and corrected emission energy maxima were located at 766 +/- 4 nm. Excited-state reduction potentials were estimated from the difference between emission energy maxima and ground-state reduction potentials. Excited-state lifetimes at room temperature in 4:1 EtOH-MeOH ranged from 167 to < 70 ns. Temperature-dependent-lifetime (90-298 K) data gave evidence for ..delta..E' values of 1100 +/- 300 cm/sup -1/. The temperature dependence was attributed to either the third MLCT state according to the localized-orbital model or the presence of a fourth CT state for (Ru(BL)/sub 2/(bpy))/sup 2 +/, since little photochemistry was found for it, and to the third and/or the fourth CT state and the dd state for both (Ru(BL)/sub 2/(bpy))/sup 2 +/ and (Ru(BL)/sub 3/)/sup 2 +/. 54 references, 7 figures, 6 tables.
- Research Organization:
- Univ. of North Carolina, Charlotte
- DOE Contract Number:
- AC05-84OR21400
- OSTI ID:
- 6808718
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:4; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
PYRIDINES
REDOX REACTIONS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES