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Title: Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(II)

Abstract

The tris complex of Ru(II) with 2,2'-dipyridylamine (HDPA) has been prepared and characterized. Luminescence spectra, lifetimes, and photoselection spectra have been measured for various protonated and deprotonated forms of the complex in aqueous and nonaqueous solution. The fully protonated (Ru(HDPA)/sub 3/)/sup 2 +/ shows a weak, broad, symmetric, and structureless emission of microsecond lifetime at low energy assigned as a dd* phosphorescence. The complexes of the deprotonated dipyridylamine ligand (DPA/sup -/) exhibit broad, asymmetric, and structureless emission at higher energy with microsecond lifetimes. The emission for these deprotonated complexes is assigned as charge-transfer IId* emission, and, as a consequence, the emission for the (Rh(DPA)/sub 2/Cl/sub 2/)/sup -/ and (Ir(DPA)/sub 2/Cl/sub 2/)/sup -/ complexes (previously reported as dII* emitters) is reconsidered. The (Ru(HDPA)/sub 2/DPA)/sup +/ and (Ru(DPA)/sub 3/)/sup -/ complex ions show spatially isolated (single-ring) emission in nonaqueous solvents; however, evidence exists that the emission for the neutral (Ru(HDPA)(DPA)/sub 2/)/sup 0/ complex is multiring in nature. Spectral data are also presented for an aquated form of the fully deprotonated complex, (Ru(DPA)/sub 3/.H/sub 2/O)/sup -/, which has also been isolated as a solid product. 10 figures, 3 tables.

Authors:
;
Publication Date:
Research Org.:
North Carolina State Univ., Raleigh
OSTI Identifier:
6201052
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem.; (United States)
Additional Journal Information:
Journal Volume: 86:19
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 08 HYDROGEN; 14 SOLAR ENERGY; RUTHENIUM COMPLEXES; CHEMICAL PREPARATION; EXCITATION; ABSORPTION SPECTRA; AMINES; CATIONS; DMSO; EMISSION SPECTRA; ETHANOL; EXPERIMENTAL DATA; LOW TEMPERATURE; MEDIUM TEMPERATURE; METHANOL; MIXED SOLVENTS; NMR SPECTRA; PHOTOIONIZATION; POLARIZATION; PYRIDINES; TEMPERATURE DEPENDENCE; TIME DEPENDENCE; WATER; ALCOHOLS; AZINES; CHARGED PARTICLES; COMPLEXES; DATA; DISPERSIONS; ENERGY-LEVEL TRANSITIONS; HETEROCYCLIC COMPOUNDS; HYDROGEN COMPOUNDS; HYDROXY COMPOUNDS; INFORMATION; IONIZATION; IONS; MIXTURES; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXYGEN COMPOUNDS; SOLVENTS; SPECTRA; SULFOXIDES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400500 - Photochemistry; 080106 - Hydrogen- Production- Biosynthesis & Photochemical Processes; 140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-)

Citation Formats

Segers, D.P., and DeArmond, M.K. Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(II). United States: N. p., 1982. Web. doi:10.1021/j100216a014.
Segers, D.P., & DeArmond, M.K. Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(II). United States. doi:10.1021/j100216a014.
Segers, D.P., and DeArmond, M.K. Thu . "Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(II)". United States. doi:10.1021/j100216a014.
@article{osti_6201052,
title = {Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(II)},
author = {Segers, D.P. and DeArmond, M.K.},
abstractNote = {The tris complex of Ru(II) with 2,2'-dipyridylamine (HDPA) has been prepared and characterized. Luminescence spectra, lifetimes, and photoselection spectra have been measured for various protonated and deprotonated forms of the complex in aqueous and nonaqueous solution. The fully protonated (Ru(HDPA)/sub 3/)/sup 2 +/ shows a weak, broad, symmetric, and structureless emission of microsecond lifetime at low energy assigned as a dd* phosphorescence. The complexes of the deprotonated dipyridylamine ligand (DPA/sup -/) exhibit broad, asymmetric, and structureless emission at higher energy with microsecond lifetimes. The emission for these deprotonated complexes is assigned as charge-transfer IId* emission, and, as a consequence, the emission for the (Rh(DPA)/sub 2/Cl/sub 2/)/sup -/ and (Ir(DPA)/sub 2/Cl/sub 2/)/sup -/ complexes (previously reported as dII* emitters) is reconsidered. The (Ru(HDPA)/sub 2/DPA)/sup +/ and (Ru(DPA)/sub 3/)/sup -/ complex ions show spatially isolated (single-ring) emission in nonaqueous solvents; however, evidence exists that the emission for the neutral (Ru(HDPA)(DPA)/sub 2/)/sup 0/ complex is multiring in nature. Spectral data are also presented for an aquated form of the fully deprotonated complex, (Ru(DPA)/sub 3/.H/sub 2/O)/sup -/, which has also been isolated as a solid product. 10 figures, 3 tables.},
doi = {10.1021/j100216a014},
journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 86:19,
place = {United States},
year = {1982},
month = {9}
}