Oxygen atom transfer in the oxidations of dimethyl sulfide and dimethyl sulfoxide by bis(bipyridine)oxo(pyridine)ruthenium(2+)

Roecker, Lee; Dobson, J. C.; Vining, William J.; Meyer, Thomas J.

doi:10.1021/ic00252a029

Cited by 90 publications

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“…Accordingly, irradiation of this solution with 355 nm light resulted in a more pronounced absorbance at 472 nm (quantum efficiency F S!O = 0.11(2)). This value is similar to that of the Obonded isomer of [Ru(bpy) 2 (py)(dmso)] 2+ (476 nm) [12] and [Ru(bpy) 2 (pic)] + (483 nm; pic = 2-pyridinecarboxylate), [14] which feature N and O donors in the Ru II (bpy) 2 coordination sphere. The S-bonded and extracted O-bonded spectra (e 472nm = 6400 cm À1 m À1 ) are shown in Figure 1.…”

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confidence: 76%

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Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

McClure

Rack

2009

Angew Chem Int Ed

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Reversible, external triggering of molecules between two ground states is central to the operation of modern molecular machines. [1][2][3] A desirable trigger is light, as it provides an ample amount of energy in a short burst of time. Although light is commonly employed for the formation of many different types of metastable states, [4][5][6][7][8] in practice it is difficult to employ light to regenerate the initial ground state. The enthalpic and entropic factors that favor the photochemical generation of the metastable state from the ground state must necessarily be disfavored for the opposing photochemical reaction. Moreover, the photoproduct often reverts to the ground state thermally. Irradiation of photochromic compounds yields metastable states that exhibit distinct electronic structures compared to their ground states.[9] Whilst a number of organic photochromic compounds feature reversible or two-color photoswitching between metastable and ground states, such reactivity is rare in transition metal complexes.[10]Herein, we report our findings on a ruthenium sulfoxide complex that features two-color photochromism.The complex [Ru(bpy) 2 (pySO)](PF 6 ) 2 (bpy = 2,2'-bipyridine, pySO = 2-(isopropylsulfinylmethyl)pyridine) was prepared from reaction of cis-[Ru(bpy) 2 Cl 2 ] with pySO. The structure and formulation of the complex was verified by oneand-two-dimensional 1 H NMR, IR spectroscopy, and elemental analysis. The 1 H NMR spectrum is consistent with the presence of two isomers, which are most likely diastereomers, as both the ruthenium and sulfur centers are chiral. Elemental analysis of the isomeric mixture supports this assignment. The lowest-energy transition in the electronic spectrum occurs at 370 nm (e = 7250 cm À1 m À1 ) and is assigned to a Ru dp!bpy p* charge-transfer transition based on its energy and intensity (Figure 1). This transition is similar to that observed for other chelating S-bonded sulfoxides.[11] Furthermore, the structurally characterized complex [Ru(bpy) 2 (py)(dmso)] 2+ (dmso = dimethylsulfoxide), which has no chelation, features a maximum absorbance at 400 nm for the S-bonded isomer.[12]Therefore, the chelate complex exhibits an additional 2000 cm À1 of stabilization relative to the non-chelate form. White light irradiation of [Ru(bpy) 2 (pySO)]2+ in propylene carbonate solution results in a decrease in the absorbance at 370 nm concomitant with an increase at 472 nm (Figure 1, inset). In accord with other ruthenium sulfoxide complexes, [13] the spectral changes indicate an intramolecular S!O isomerization, with an isosbestic point at 408 nm. However, the observed spectral changes are muted in comparison to these other complexes. We questioned whether or not this spectrum represented a photostationary state. Accordingly, irradiation of this solution with 355 nm light resulted in a more pronounced absorbance at 472 nm (quantum efficiency F S!O = 0.11(2)). This value is similar to that of the Obonded isomer of [Ru(bpy) 2 (py)(dmso)] 2+ (476 nm) [12] and [Ru(bpy) 2 (pic)] + (483...

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confidence: 76%

“…[11] Furthermore, the structurally characterized complex [Ru(bpy) 2 (py)(dmso)] 2+ (dmso = dimethylsulfoxide), which has no chelation, features a maximum absorbance at 400 nm for the S-bonded isomer. [12] Therefore, the chelate complex exhibits an additional 2000 cm À1 of stabilization relative to the non-chelate form. White light irradiation of [Ru(bpy) 2 …”

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confidence: 99%

Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

McClure

Rack

2009

Angew Chem Int Ed

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“…This complex is reminiscent of a report from Meyer regarding [Ru(bpy) 2 (py)(dmso)] 2+ (py is pyridine), [76] where both S-and O-bonded isomers are observed from reaction of [(bpy) 2 Figure 8]. [38] The infrared spectrum provides structural evidence for isomerization.…”

Section: (Pyso)]supporting

confidence: 64%

Isomerization in Photochromic Ruthenium Sulfoxide Complexes

McClure

Rack

2010

Eur J Inorg Chem

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The spectroscopic properties of photochromic ruthenium sulfoxide complexes are reviewed. The mode of action is associated with an excited state SǞO isomerization triggered by light. These complexes feature large, positive Ru 3+/2+ reduction potentials indicative of stabilization of the Ru dπ orbital set. In addition, these compounds feature large quantum yields of isomerization. In aggregate, the data argue

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“…Experimentally, both the S-linked [46] and the O-linked [47] isomers have been previously characterized but in none of these studies, all carried out in solution, evidences of S/O (or O/S) linkage isomerization were found.…”

Section: Photo-triggered Isomerization Of [Ru(bpy)(tpy)dmso] + : Expementioning

confidence: 99%

“…2+ [48], was an intramolecular process as the dmso ligand was kept confined within the direct coordination sphere of the metal atom [47].…”

Section: Photo-triggered Isomerization Of [Ru(bpy)(tpy)dmso] + : Expementioning

confidence: 99%

Theoretical modelling of photoactive molecular systems: insights using the Density Functional Theory

Ciofini

Lainé

Bedioui

et al. 2005

Comptes Rendus. Chimie

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An account of the performance of a modern and efficient approach to Density Functional Theory (DFT) for the prediction of the photophysical behavior of a series of Ru(II) and Os(II) complexes is given. The time-dependent-DFT method was used to interpret their electronic spectra. Two different types of compounds have been analyzed: (1) a complex undergoing a light induced isomerization of one of its coordination bonds; (2) an inorganic dyads expected to undergo intramolecular photoinduced electron transfer to form a charge separated (CS) sate. Besides the noticeable quantitative agreement between computed and experimental absorption spectra, our results allow to clarify, by first principles, both the nature of the excited states and the photochemical behavior of these complex systems, thus underlying the predictive character of the theoretical approach. RésuméNous rendons compte ici des performances d'une approche moderne et opérante de la théorie de la fonctionnelle de la densité (DFT) pour la prédiction du comportement photophysique de composés du ruthénium (II) et de l'osmium(II). Pour interpréter leurs propriétés d'absorption électronique, l'approche DFT dépendante du temps a été utilisée. Nous illustrons notre propos par l'analyse des deux systèmes suivants : (1) un complexe qui présente une isomérisation photo-induite de la liaison de coordination impliquant l'un de ses ligands ; (2) une molécule bipartite composée d'un complexe photosensibilisateur lié à un accepteur d'électron, conçue pour être le siège d'un transfert d'électron photo-induit conduisant à la formation d'un état de « charges séparées » (CS). Au-delà du remarquable accord quantitatif constaté entre les caractéristiques calculées et expérimentales des spectres d'absorption, nos résultats ont permis de clarifier, ab initio, la nature des états excités impliqués, illustrant ainsi les vertus prédictives de l'approche théorique employée.

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Oxygen atom transfer in the oxidations of dimethyl sulfide and dimethyl sulfoxide by bis(bipyridine)oxo(pyridine)ruthenium(2+)

Cited by 90 publications

References 0 publications

Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

Isomerization in Photochromic Ruthenium Sulfoxide Complexes

Theoretical modelling of photoactive molecular systems: insights using the Density Functional Theory

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