Stereoisomers of mono-, di-, and triruthenium(II) complexes containing the bridging ligand 1,4,5,8,9,12-hexaazatriphenylene and studies of their photophysical properties

Rutherford, Todd J., Van Gijte, Olivia, Mesmaeker, Andrée Kirsch-De, and Keene, F. Richard (1997) Stereoisomers of mono-, di-, and triruthenium(II) complexes containing the bridging ligand 1,4,5,8,9,12-hexaazatriphenylene and studies of their photophysical properties. Inorganic Chemistry, 36 (20). pp. 4465-4474.

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Abstract

A combination of synthetic methods involving mononuclear precursors of predetermined chirality {Δ- or Λ-[Ru(pp)₂(CO)₂]²⁺; pp = 2,2'-bipyridine or 1,10-phenanthroline} and chromatographic techniques has allowed the isolation of the meso (ΔΛ) and rac (ΔΔ/ΛΛ) diastereoisomers of the dinuclear complexes [{Ru(pp)₂}₂(μ-HAT)]⁴⁺ {HAT = 1,4,5,8,9,12-hexaazatriphenylene}. The enantiomers of the rac forms have been separated, and characterization of all species has been achieved by NMR and CD studies. Additonally, the homochiral (Δ³/Λ³) and heterochiral (Δ²Λ/Λ²Δ) diastereoisomers of the trinuclear complexes [{Ru(pp)₂}₃(μ-HAT)]⁶⁺, and the enantiomers of both forms, have been isolated and identified. Emission studies of all the dinuclear species at room temperature indicate the relative luminescence quantum yields and the emission lifetimes significantly decrease for the meso compared with the rac diastereoisomers. No significant differences were detected at room temperature in the diastereoisomeric forms of the trinuclear compounds. However, in a glass at low temperature (80 K), the luminescence lifetimes of the trinuclear heterochiral diastereoisomer were slightly shorter than those of the homochiral form.

Item ID: 22815
Item Type: Article (Refereed Research - C1)
Keywords: ruthenium(II) complexes; polypyridine complexes; dna; luminescence; 1,4,5,8-tetraazaphenanthrene; electrochemistry; rhodium(III); absorption; oxidation; series
ISSN: 1520-510X
Date Deposited: 09 Aug 2012 05:35
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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