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- Ott, S., et al.
(författare)
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Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer : Synthesis and photophysical properties
- 2004
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 43:15, s. 4683-4692
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Tidskriftsartikel (refereegranskat)abstract
- A model of the iron hydrogenase active site with the structure [(mu-ADT)Fe-2(CO)(6)] (ADT = azadithiolate (S-CH2-NR-CH2-S), (2: R = 4-bromophenyl, 3: R = 4-iodophenyl)) has been assembled and covalently linked to a [Ru(terpy)(2)](2+) photosensitizer. This trinuclear complex 1 represents one synthetic step toward the realization of our concept of light-driven proton reduction. A rigid phenylacetylene tether has been incorporated as the linking unit in 1 in order to prolong the lifetime of the otherwise short-lived [Ru(terpy)(2)](2+) excited state. The success of this strategy is demonstrated by comparison of the photophysical properties of 1 and of two related ruthenium complexes bearing acetylenic terpyridine ligands, with those of [Ru(terpy)(2)](2+). IR and electrochemical studies reveal that the nitrogen heteroatom of the ADT bridge has a marked influence on the electronic properties of the [Fe-2(CO)(6)] core. Using the Rehm-Weller equation, the driving force for an electron transfer from the photoexcited *[Ru(terpy)(2)](2+) to the diiron site in 1 was calculated to be uphill by 0.59 eV. During the construction of the trinuclear complex 1, n-propylamine has been identified as a decarbonylation agent on the [(mu-ADT)Fe-2(CO)(6)] portion of the supermolecule. Following this procedure, the first azadithiolate-bridged dinuclear iron complex coordinated by a phosphine ligand [(mu-ADT)Fe-2(CO)(5)PPh3] (4, R = 4-bromophenyl) was synthesized.
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- Sun, Licheng C., et al.
(författare)
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Iron hydrogenase active site mimics in supramolecular systems aiming for light-driven hydrogen production
- 2005
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Ingår i: Coordination chemistry reviews. - : Elsevier BV. - 0010-8545 .- 1873-3840. ; 249:15-16, s. 1653-1663
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Forskningsöversikt (refereegranskat)abstract
- Models of the iron hydrogenase active site [(mu-DT)Fe-2(CO)(6)] (DT: dithiolate) have been synthesized where the dithiolate co-factor bears a functional group to allow for their incorporation into supramolecular systems. Covalently linked to ruthenium(II) polypyridyl photosensitizers, the resulting ruthenium-diiron complexes represent the first members of a new class of dyads designed to promote the light-driven production of hydrogen. The functionalized diiron complexes have been characterized by X-ray crystallography. The redox properties of all complexes were investigated by cyclic voltammetry and the interactions between the photo-excited ruthenium moiety and the diiron unit in these dyads were evaluated by time-resolved spectroscopy.
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