Visible spectra of dicarbonyl substituted tris-bipyridyl ruthenium(II) complexes

Ford, William E.; Calvin, Melvin

doi:10.1016/0009-2614(80)80614-2

Cited by 19 publications

(14 citation statements)

References 21 publications

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“…To circumvent this diffusion limitation, and with the aim of probing the reduced forms of 1 after excitation of the sample, we synthesized an amphiphilic analogue of the PS Ru amph 2+ (as [Ru(bpy) 2 {5,5′‐(CONHC 12 H 25 ) 2 bpy}]Cl 2 ; Figure ) that could be incorporated into vesicles by supramolecular self‐assembly, as shown by König et al . Because the UV/Vis absorption spectrum of this Ru 2+ complex shifts upon changing the polarity of its chemical environment, we could track the uptake of Ru amph 2+ by the vesicles (up to 0.9 m m PC to 0.1 m m Ru amph 2+ ). The D H at maximum intensity of the PC vesicles was 103 nm, which increased to 112 nm upon addition of the PS.…”

Section: Resultsmentioning

confidence: 99%

“…Because the UV/Vis absorption spectrum of this complex was sensitive to the polarity of its chemical environment, we tracked the UV/Vis spectral changes upon the addition of vesicles (up to 0.9 m m PC ) to an aqueous solution of 0.1 m m Ru amph 2+ . (A proper supramolecular titration was not possible because the absolute absorption values were irreproducible due to light scattering from the vesicles.)…”

Section: Methodsmentioning

confidence: 99%

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Photocatalytic Hydrogen Generation by Vesicle‐Embedded [FeFe]Hydrogenase Mimics: A Mechanistic Study

Becker

Bouwens

Schippers

et al. 2019

Chemistry A European J

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Artificial photosynthesis—the direct photochemical generation of hydrogen from water—is a promising but scientifically challenging future technology. Because nature employs membranes for photodriven reactions, the aim of this work is to elucidate the effect of membranes on artificial photocatalysis. To do so, a combination of electrochemistry, photocatalysis, and time‐resolved spectroscopy on vesicle‐embedded [FeFe]hydrogenase mimics, driven by a ruthenium tris‐2,2′‐bipyridine photosensitizer, is reported. The membrane effects encountered can be summarized as follows: the presence of vesicles steers the reactivity of the [FeFe]‐benzodithiolate catalyst towards disproportionation, instead of protonation, due to membrane characteristics, such as providing a constant local effective pH, and concentrating and organizing species inside the membrane. The maximum turnover number is limited by photodegradation of the resting state in the catalytic cycle. Understanding these fundamental productive and destructive pathways in complex photochemical systems allows progress towards the development of efficient artificial leaves.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Photocatalytic Hydrogen Generation by Vesicle‐Embedded [FeFe]Hydrogenase Mimics: A Mechanistic Study

Becker

Bouwens

Schippers

et al. 2019

Chemistry A European J

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“…2). Ru(bipy)2+ derivatives have a marked solvent dependency of their optical absorption and emission spectra (16). Consequently, the polarity of the environment of the chromophore could be assessed from the shape of the spectrum.…”

Section: Resultsmentioning

confidence: 99%

Photosensitized production of hydrogen by hydrogenase in reversed micelles

Hilhorst

Laane

Veeger

1982

Proc. Natl. Acad. Sci. U.S.A.

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Hydrogenase (hydrogen:ferricytochrome c3 oxidoreductase, EC 1. 12.2. 1) from Desulfovibrio vulgaris was encapsulated in reversed micelles with cetyltrimethylammonium bromide as surfactant and a chloroform/octane mixture as solvent. Reducing equivalents for hydrogenase-catalyzed hydrogen production were provided-by vectorial photosensitized electron.transfer from a donor (thiophenol) in the organic phase through a surfactant-Ru2, sensitizer located in the interphase to methyl viologen concentrated in the aqueous core ofthe reversed micelle. The results show that reversed micelies provide a microenvironment that (i) stabilizes hydrogenase against inactivation and (ii) allows an efficient vectorial photosensitized electron and proton flow from the organic phase to hydrogenase in the aqueous phase.It has been well established that surfactant molecules dissolved in organic solvents aggregate to reversed micelles in the presence of small amounts of water. Reversed micelles are of multiple interest for they create a microenvironment that provides a unique reaction medium.An area of active current research is the photochemical investigation of these organized structures with the aim of obtaining structural characteristics (1-3) and of modeling natural processes such as photosynthesis (4-6). The latter objective is of particular interest because it includes potential applications such as solar energy conversion and storage. Essential for efficient solar energy conversion and storage is the separation of photoproducts formed in photosensitized electron transfer reactions. Recently, Willner et aL (5) showed that effective separation ofphotoproducts can be achieved in a reversed micellar system by vectorial photosensitized electron transfer from a donor in the organic phase to an acceptor in the water pool and vice versa.In addition, the application of reversed micelles in enzyme catalysis increases. Reversed micelles have been shown to provide a microenvironment for enzymes that protects them from the unfavorable action of organic solvents by means of surfactants. Hence, the study of structural and catalytic properties of enzymes can be extended to organic media. To date, several enzymes, such as trypsin, a-chymotrypsin, lactate dehydrogenase, peroxidase, and lysozyme have been encapsulated in the aqueous core of reversed micelles (7-9).In this study we entrapped hydrogenase (hydrogen:ferricytochrome c3 oxidoreductase, EC 1.12.2.1) from Desulfovibrio vulgaris in a reversed cetyltrimethylammonium bromide micelle; the objective was to obtain a highly organized system for an efficient coupling between hydrogenase and a photochemical system that produces reducing equivalents and protons necessary for hydrogenase action.

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“…We assign this absorption to the dπ(Re)Ǟπ* (heterocyclic ligand) transition. [16] Note that on going from 2 to 1 the lowest-energy absorption band shifts to considerably higher energies (from 432 to 358 nm). This may be attributed to the different electronic properties of the coordinated naphthyridylamido and -carbamoyl groups.…”

Section: Crystal Structuresmentioning

confidence: 98%

Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) Complex

Zuo

Che

et al. 2002

Eur J Inorg Chem

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Visible spectra of dicarbonyl substituted tris-bipyridyl ruthenium(II) complexes

Cited by 19 publications

References 21 publications

Photocatalytic Hydrogen Generation by Vesicle‐Embedded [FeFe]Hydrogenase Mimics: A Mechanistic Study

Photocatalytic Hydrogen Generation by Vesicle‐Embedded [FeFe]Hydrogenase Mimics: A Mechanistic Study

Photosensitized production of hydrogen by hydrogenase in reversed micelles

Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) Complex

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