Unique spectroscopic properties of mixed-ligand complexes with 2,2'-dipyridylamine: a dual luminescence from a ruthenium(II) complex

The 77 K absorption, emission, excitation, photoselection, and time-resolved emission spectra and emission lifetimes were obtained in aprotic and protic systems for the series of complexes (Ru(bpy)/sub n/(HDPA)/sub 3-n/)/sup 2 +/ (n = 0-3) and (Ru-(phen)/sub n/(HDPA)/sub 3-n/)/sup 2 +/ (n = 0-3). Th...

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Veröffentlicht in:J. Am. Chem. Soc.; (United States) 1987-08, Vol.109 (16), p.4895-4901
Hauptverfasser: Blakley, Richard L, DeArmond, M. Keith
Format: Artikel
Sprache:eng
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Zusammenfassung:The 77 K absorption, emission, excitation, photoselection, and time-resolved emission spectra and emission lifetimes were obtained in aprotic and protic systems for the series of complexes (Ru(bpy)/sub n/(HDPA)/sub 3-n/)/sup 2 +/ (n = 0-3) and (Ru-(phen)/sub n/(HDPA)/sub 3-n/)/sup 2 +/ (n = 0-3). The n = 2 species have d-..pi..* MLCT emission characteristics indicative of the Ru-bpy and Ru-phen chromophores as do the n = 1 species in water, but in weak hydrogen-bonding solvents, as well as aprotic solvents, a second emission is observed producing a dual luminescence for the n = 1 species. This second emission is assigned to an n/sub HDPA/-..pi../sub bpy/* (or n/sub HDPA/-..pi../sub phen/*) interligand charge-transfer (ILCT) process. The absorption spectra for the deprotonated species (Ru(bpy)/sub n/(DPA/sup -/)/sub 3-n/)/sup (n-1)+/ (n = 1,2) were also obtained, and the absence of emission up to 800 nm for these complexes is discussed in terms of available emitting states and metal perturbations.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00250a023