Stereoisomers in heterometallic (Ru2Os) and heteroleptic homometallic (RuRu′Ru″) trinuclear complexes incorporating the bridging ligand hat (1,4,5,8,9,12-hexaazatriphenylene) ‡

Rutherford, Todd J.; Keene, F. Richard

doi:10.1039/a707122a

Cited by 29 publications

(33 citation statements)

References 31 publications

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“…Synthesis and stereoisomer separation: The synthetic strategies for the stereoisomerically pure di-{meso (DL) and rac (DD and LL)} and trinuclear {homochiral (D 3 and L 3 ) and heterochiral (D 2 L and L 2 D)} systems have been reported previously, [16,17,37] and were based upon a combination of stereoretentive and chromatographic methodologies. [14,15] Electrochemistry: The electrochemical properties of the stereoisomeric forms [17] of [{Ru(bpy) 2 } 2 (m-hat)] n + and [{Ru-(bpy) 2 } 3 (m-hat)] n + as well as the stereoisomeric mixtures [24,38] of [{Ru(bpy) 2 } 2 (m-hat)] 4 + and [{Ru(bpy) 2 } 3 (m-hat)] 6 + have been reported previously.…”

Section: Resultsmentioning

confidence: 99%

Intervalence Charge Transfer (IVCT) in Ruthenium Dinuclear and Trinuclear Assemblies Containing the Bridging Ligand HAT {1,4,5,8,9,12‐hexaazatriphenylene}

D’Alessandro

Keene

2005

Chemistry A European J

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The IVCT characteristics of the mixed-valence forms of the dinuclear [{Ru(bpy)(2)}(2)(mu-hat)](n+) and the trinuclear [{Ru(bpy)(2)}(3)(mu-hat)](n+) species {HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2'-bipyridine} show a marked dependence on the nuclearity, and in the trinuclear case on the extent of oxidation. Small differences are also found between the diastereoisomers of the dinuclear complex {meso (DeltaLambda) and rac (DeltaDelta/LambdaLambda)}, and between the homochiral (Delta(3)/Lambda(3)) and heterochiral (Delta(2)Lambda/Lambda(2)Delta) diastereoisomers of the trinuclear case. The strong metal-metal interactions result in unusual spectroscopic and electrochemical properties of the singly-oxidised (+7) and doubly-oxidised (+8) trinuclear mixed-valence species. A qualitative localised bonding description based on the geometrical properties of the dpi(Ru(II/III)) orbitals is invoked to explain the IVCT behaviour in the di- and trinuclear systems.

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Section: Resultsmentioning

confidence: 99%

Intervalence Charge Transfer (IVCT) in Ruthenium Dinuclear and Trinuclear Assemblies Containing the Bridging Ligand HAT {1,4,5,8,9,12‐hexaazatriphenylene}

D’Alessandro

Keene

2005

Chemistry A European J

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“…The parent compound of this series, 1,4,5,8,9,12-hexaazatriphenylene (HAT), has recently been reported to form a robust (10,3)-a network containing chiral micropores on coordinating Ag I (Abrahams et al, 1998). The chemistry of ruthenium(II) (Kirsch±De Mesmaeker et al, 1989;Rutherford et al, 1997) and mixed Ru II /Os II (Rutherford & Keene, 1998) complexes of HAT have also been studied. The hexaphenyl derivative of HAT has been used to form a number of capped polymetallic complexes with copper(I) and silver(I) Baxter, Lehn, Baum et al, 1993;Baxter, Lehn, Kneisel et al, 1999).…”

Section: Commentmentioning

confidence: 99%

1,6,7,12,13,18-Hexaazatrinaphthylene tetrachloroform solvate

Alfonso

Stœckli-Evans

2001

Acta Cryst E

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The title compound, 1,6,7,12,13,18‐hexaazatrinaphthylene (HATN) tetrachloroform solvate, C24H12N6·4CH3Cl, belongs to a series of planar bridging ligands with an extensive delocalized π‐electron system. The planar molecules pack in pairs with a π–π stacking of a symmetry‐related quinoline moiety and are surounded by solvent molecules of chloroform. The latter are involved in C—H⋯N contacts with the six pyrazine N atoms.

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“…[9][10][11][12] In order to bring these individual units together within a larger assembly, it is of considerable importance to be able to control the spatial arrangement of both the ligands and the metal centres in relation to one another. It has been demonstrated that the distance between and the orientation of individual groups within larger assemblies can have small but significant effects on the electrochemistry and on the excitedstate lifetimes, 13, 14 and consequently their potential use as photosensitisers. The isolation of single isomeric forms also has great implication on the ease of characterisation by NMR spectroscopy and simplifies the art of crystal growth for X-ray structural analysis.…”

Section: Introductionmentioning

confidence: 99%

The isolation and purification of tris-2,2′-bipyridine complexes of ruthenium(ii) containing unsymmetrical ligands

Fletcher

Nieuwenhuyzen

Rainey

2001

J. Chem. Soc., Dalton Trans.

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Monomeric ruthenium() complexes [Ru(L) 3 ] 2ϩ containing unsymmetric bipyridine ligands [Where L = 5-methyl-2,2Ј-bipyridine (L 1 ), 5-ethyl-2,2Ј-bipyridine (L 2 ), 5-propyl-2,2Ј-bipyridine (L 3 ), 5-(2-methylpropyl)-2,2Ј-bipyridine (L 4 ), 5-(2,2-dimethylpropyl)-2,2Ј-bipyridine (L 5 ) or 5-(carbomethoxy)-2,2Ј-bipyridine (L 6 )] have been studied and the meridional and facial isomers isolated by the use of cation-exchange column chromatography (SP Sephadex C-25) eluting with either sodium toluene-4-sulfonate or sodium hexanoate. The relative yield of the facial isomer was found to decrease with increasing steric bulk, preventing the isolation of fac-[Ru(L 5 ) 3 ] 2ϩ . The two isomeric forms were characterized by 1 H NMR spectroscopy, with the complexes [Ru(L 1-3 ) 3 ] 2ϩ demonstrating an unusually large coupling between the H 6 and H 4 protons. Crystals suitable for X-ray structural analysis of [Ru(L 1 ) 3 ] 2ϩ were obtained as a mixture of the meridional and facial isomers, indicating that separation of this isomeric mixture could not be achieved by fractional crystallisation. The optical isomers of the complex [Ru(L 3 ) 3 ] 2ϩ were chromatographically separated on SP Sephadex C-25 relying upon the inherent chirality of the support. It is apparent that chiral interactions can inhibit geometric isomer separation using this technique.

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Stereoisomers in heterometallic (Ru2Os) and heteroleptic homometallic (RuRu′Ru″) trinuclear complexes incorporating the bridging ligand hat (1,4,5,8,9,12-hexaazatriphenylene) ‡

Cited by 29 publications

References 31 publications

Intervalence Charge Transfer (IVCT) in Ruthenium Dinuclear and Trinuclear Assemblies Containing the Bridging Ligand HAT {1,4,5,8,9,12‐hexaazatriphenylene}

Intervalence Charge Transfer (IVCT) in Ruthenium Dinuclear and Trinuclear Assemblies Containing the Bridging Ligand HAT {1,4,5,8,9,12‐hexaazatriphenylene}

1,6,7,12,13,18-Hexaazatrinaphthylene tetrachloroform solvate

The isolation and purification of tris-2,2′-bipyridine complexes of ruthenium(ii) containing unsymmetrical ligands

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