Synthesis, Characterization, and Intervalence Charge Transfer Properties of a Series of Rhenium(I)−Iron(III) Mixed-Valence Compounds

Pfennig, Brian W.; Cohen, Jamie L.; Sosnowski, Irene; Novotny, Nathan M.; Ho, Douglas M.

doi:10.1021/ic9811751

Cited by 26 publications

(29 citation statements)

References 34 publications

(32 reference statements)

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“…Further, double coordination of BL lowers the π* BL orbital, such that each binding site may couple more efficiently with individual metal core. The observed trend i.e., the decrease in metal-metal interaction with increase in the distance that separates them matches with theoretical prediction on the basis of MO calculations 22,23 24 . For complexes, VI and VII, there exist an interrupted π-electron system and thus no orbital pathway is available for metal-metal interaction and hence no IVCT transition band.…”

Section: Intervalence Electron Transfersupporting

confidence: 83%

Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

2002

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Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating Ru(III) and Fe(II)-centres linked by various saturated and unsaturated bridging ligands (BL). Studies reveal that degree of ground state electronic interaction and coupling between Ru(III) and Fe(II)-centres can be attenuated by changing the nature of the bridging ligand. Further, inclusion of the bridging ligand with interrupted π-electron system in a β-CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

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Section: Intervalence Electron Transfersupporting

confidence: 83%

Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

2002

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“…Accordingly, the predicted blue-shift in the energies of the absorption bands is observed, and is consistent with previous literature reports for IVCT transitions in related di-and trinuclear systems. [72] The~3000 cm À1 separation between the bands assigned as IVCT transitions is not consistent with their interpretation based on spin-orbit coupling components however, and indicates that a molecular orbital approach-which includes vibronic coupling-may be essential.…”

mentioning

confidence: 80%

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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“…This is consistent with previous observations for the +7 and +8 states for the trinuclear l-HAT complex, 41 and with previous literature reports for IVCT transitions in related di-and trinuclear systems. 83 The assignment of the bands in the region at energies lower than 7000 cm −1 is ambiguous due to the presence of comproportionation equilibria, however these may be reasonably ascribed to the residual absorptions of the mono-oxidised +7 species.…”

Section: Intervalence Charge Transfermentioning

confidence: 99%

Intervalence charge transfer in a “chain-like” ruthenium trinuclear assembly based on the bridging ligand 4,7-phenanthrolino-5,6:5′,6′-pyrazine (ppz)

D’Alessandro

Keene

2006

Dalton Trans.

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The IVCT characteristics of the mixed valence forms of the trinuclear complex [{Delta-Ru(bpy)2}2{Delta(t)-Ru(bpy)(mu-ppz)2}]n+ (n = 7, 8; t = trans), and the diastereoisomers (meso and rac) of the dinuclear complex [{Ru(bpy)2}2(mu-ppz)]5+, display a marked dependence on the nuclearity and extent of oxidation of the assemblies. The dinuclear species are classified as borderline localised-delocalised mixed valence species while the two mixed valence states of the trinuclear complex exhibit localised behaviour. One-electron oxidation of a terminal Ru centre in the trinuclear case gives rise to a broad, low intensity IVCT band for the +7 mixed valence species which is composed of two underlying Gaussian-shaped bands. The transitions are identified as adjacent and remote IVCT transitions, with the former dominating the intensity of the IVCT manifold. The +8 mixed valence species exhibits a single dominant IVCT band arising from the equivalent IVCT transitions from the central Ru(II) to peripheral Ru(III) centres.

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Synthesis, Characterization, and Intervalence Charge Transfer Properties of a Series of Rhenium(I)−Iron(III) Mixed-Valence Compounds

Cited by 26 publications

References 34 publications

Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

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 in a “chain-like” ruthenium trinuclear assembly based on the bridging ligand 4,7-phenanthrolino-5,6:5′,6′-pyrazine (ppz)

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