Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer: Synthesis and photophysical properties

Sascha Ott, Magnus Borgström, Mikael Kritikos, Reiner Lomoth, Jonas Bergquist, Björn Åkermark, Leif Hammarström, Licheng Sun

Research output: Contribution to journalArticle

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Abstract

A model of the iron hydrogenase active site with the structure [μ-ADT)Fe2(CO)6] (ADT = azadithiolate (S-CH 2-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 [Fe2(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 [(μ-ADT)Fe2(CO)6] portion of the supermolecule. Following this procedure, the first azadithiolate-bridged dinuclear iron complex coordinated by a phosphine ligand [(μ-ADT)Fe 2(CO)5PPh3] (4, R = 4-bromophenyl) was synthesized.

Original languageEnglish
Pages (from-to)4683-4692
Number of pages10
JournalInorganic Chemistry
Volume43
Issue number15
DOIs
Publication statusPublished - Jul 26 2004

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Photosensitizing Agents
Ruthenium
Carbon Monoxide
ruthenium
iron
ligands
phosphine
synthesis
phosphines
electron transfer
Bearings (structural)
Propylamines
methylidyne
Ligands
nitrogen
life (durability)
protons
electronics
Excited states
Electronic properties

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ott, S., Borgström, M., Kritikos, M., Lomoth, R., Bergquist, J., Åkermark, B., ... Sun, L. (2004). Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer: Synthesis and photophysical properties. Inorganic Chemistry, 43(15), 4683-4692. https://doi.org/10.1021/ic0303385

Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer : Synthesis and photophysical properties. / Ott, Sascha; Borgström, Magnus; Kritikos, Mikael; Lomoth, Reiner; Bergquist, Jonas; Åkermark, Björn; Hammarström, Leif; Sun, Licheng.

In: Inorganic Chemistry, Vol. 43, No. 15, 26.07.2004, p. 4683-4692.

Research output: Contribution to journalArticle

Ott, Sascha ; Borgström, Magnus ; Kritikos, Mikael ; Lomoth, Reiner ; Bergquist, Jonas ; Åkermark, Björn ; Hammarström, Leif ; Sun, Licheng. / Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer : Synthesis and photophysical properties. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 15. pp. 4683-4692.
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