Photoredox behavior of a trinuclear Ru(III),Ru(II),Co(III) complex induced by metal-to-metal charge transfer excitations

Kunkely, Horst; Pawlowski, Valeri; Vogler, Arnd

doi:10.1016/0020-1693(94)04021-4

Cited by 19 publications

(10 citation statements)

References 34 publications

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“…The number of unsymmetrical trinuclear complexes is still so low that those which were isolated and fully characterized can all be shown: [(py)(NH 3 ) 4 Ru᎐NC᎐Ru(bipy) 2 ᎐CN᎐Ru(NH 3 ) 5 ] 6ϩ 11 (py = pyridine), 62 [(phen)(CO) 3 Re᎐CN᎐Ru(bipy) 2 ᎐CN᎐Ru-(bipy) 2 CN] 2ϩ 12 (phen = 1,10-phenanthroline), 72 [(H 3 N) 5 Co᎐ NC᎐Co(CN) 4 ᎐CN᎐Ru(CN) 5 ] 3Ϫ 13, 57 [(H 3 N) 5 Ru᎐NC᎐Ru(CN) 4 ᎐ CN᎐Co(NH 3 ) 5 ] 2ϩ 14 58 and [Cp(dppe)Fe᎐NC᎐Pt(CN) 2 ᎐CN᎐Ru-(PPh 3 ) 2 Cp] 15. 88 The lability of some of the classical complexes made their handling difficult.…”

Section: Chainsmentioning

confidence: 99%

“…This was observed for the Co III Co III Ru II complex 13 decomposing to Co II and cyano complexes of Co III and Ru III , 57 as well as for the Ru III Ru II Co III complex 14 decomposing to Co II and complexes of Ru III . 58 A reaction type which is common in other fields of photochemistry, the radical attack on solvents by photoredoxgenerated odd-electron species, seems to have been observed in only one case so far for oligonuclear metallocyanides. The intermediate Ti III species produced by the photolytic disproportionation of [Cp 2 Ti IV {NC᎐Ru II (CN) 5 } 2 ] 6Ϫ 52 {producing [Ru III -(CN) 6 ] 3Ϫ as the by-product} attacks the solvent CHCl 3 and abstracts a chlorine atom regenerating the Ti IV state.…”

Section: Photoredox Reactionsmentioning

confidence: 99%

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Cyanide-bridged oligonuclear complexes: features and attractions †

Vahrenkamp¹,

Gei²,

Richardson³

1997

J. Chem. Soc., Dalton Trans.

176

131

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The synthetic and structural chemistry as well as some physical and chemical properties of cyanide-bridged complexes containing two or more metal building blocks are discussed. Emphasis is laid on molecular shape and design and their consequences, including the effects of cyanide-isocyanide isomerism. Redox phenomena and molecular magnetism have been dealt with in relation to electronic communication across the cyanide bridges and metal-metal charge transfer. Long-range interactions between remote metal centers are discussed, and the few cases where they lead to remote chemical reactions are listed.Prussian Blue, [Fe 4 {Fe(CN) 6 } 3 ]ؒxH 2 O, which actually is the oldest known co-ordination compound, 1 has attracted the skills of many scientists seeking an understanding of its formation and composition, 2 structure, 3 colour 4 and physical properties like magnetism 5 and electrical conductivity. 6 Although it was soon obvious that the linking of two different metal ions by the cyanide ligand is the basis of all these phenomena, this did not initiate a variation of the theme. The systematic synthetic and physical exploration of Prussian Blue-like compounds had to await the popularity of the chemistry of materials. Only in recent years has a number of attractive two-and three-dimensional co-ordination polymers comprised of M᎐CN᎐MЈ units been prepared and subjected to the appropriate measurements. 7 While bulk magnetism and conductivity require extended interactions their basic fundamental property, the electronic communication between two metals across the cyanide bridge, is local and can be studied in simple dinuclear complexes. But classical co-ordination chemistry was not interested in this phenomenon, and hence the literature of more than 25 years ago contains only rare examples of cyanide-bridged systems 8 amongst the multitude of ligand-bridged dinuclear complexes. 9 It took the emerging discussion of mixed valence 10-12 and innersphere electron transfer 13,14 to move the M᎐CN᎐MЈ systems into the limelight. They were among the first to be studied in this respect, 15,16 and since then the electronic interactions between two metals across a cyanide bridge have proven to be a fertile area of research.In the last 15 years many di-and tri-nuclear complexes with bridging cyanide ligands have been investigated for the electronic communication and the electron transfer between their metal centers by means of electronic spectroscopy, electrochemistry, IR spectroscopy, fast kinetic methods and molecular orbital (MO) theory. Among others, the research groups of

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Section: Chainsmentioning

confidence: 99%

Section: Photoredox Reactionsmentioning

confidence: 99%

Cyanide-bridged oligonuclear complexes: features and attractions †

Vahrenkamp¹,

Gei²,

Richardson³

1997

J. Chem. Soc., Dalton Trans.

176

131

View full text Add to dashboard Cite

show abstract

“…This work, which has also been pursued by the research groups of Haim, [8] Connelly, [9] Vogler, [10] Scandola [11] and Denning, [12] originates from the observation that a bridging cyanide is a good conductor of electronic interactions between the metallic groups attached to it. In this context it is not so much the bulk properties like magnetism, luminescence or electrical conductivity that interest us, but the phenomena which result from metalmetal charge transfer like multi-redox steps, mixed valence and long-range electronic interactions.…”

Section: Introductionmentioning

confidence: 97%

Cyanide‐Bridged Oligonuclear Complexes Containing Ni‐CN‐Cu and Pt‐CN‐Cu Linkages

Flay

Vahrenkamp

2003

Eur J Inorg Chem

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“…the typical value for ion pairs. 1-9 The rate constant k et for the thermal electron-transfer process 35 [equation (9)] can be expressed as in equation (12), where κ el is the electronic…”

Section: Resultsmentioning

confidence: 99%

“…transition and χ is the reorganization energy. The term ∆E represents the degree of electronic asymmetry and is the free energy for the related thermal redox reaction(9). It can be estimated from the formal redox poten-{[Pt II (NH 3 ) 4 ] 2+ ,[W V (CN) 8 ] 3Ϫ } {[Pt III (NH 3 ) 4 ] 3+ ,[W IV (CN) 8 ] 4Ϫ } (9)tial of the redox couples involved,∆E = E ₂  ₁ [W(CN) 8 3Ϫ/4Ϫ ] Ϫ E ₂  ₁ [Pt(NH 3) 4 3+/2+ ].…”

mentioning

confidence: 99%

New donor–acceptor system based on [Pt(NH3)4]2+ and [W(CN)8]3− ions

Sieklucka¹

1997

J. Chem. Soc., Dalton Trans.

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Photoredox behavior of a trinuclear Ru(III),Ru(II),Co(III) complex induced by metal-to-metal charge transfer excitations

Cited by 19 publications

References 34 publications

Cyanide-bridged oligonuclear complexes: features and attractions †

Cyanide-bridged oligonuclear complexes: features and attractions †

Cyanide‐Bridged Oligonuclear Complexes Containing Ni‐CN‐Cu and Pt‐CN‐Cu Linkages

New donor–acceptor system based on [Pt(NH3)4]2+ and [W(CN)8]3− ions

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