Bio-inspired, side-on attachment of a ruthenium photosensitizer to an iron hydrogenase active site model

• The first ruthenium - diiron complex [(mu- pdt) Fe-2(CO)(5){PPh2(C(6)H(4)CCbpy)} Ru(bpy)(2)](2+) 1 (pdt = propyldithiolate, bpy = 2,2'-bipyridine) is described in which the photoactive ruthenium trisbipyridyl unit is linked to a model of the iron hydrogenase active site by a ligand directly attached to one of the iron centers. Electrochemical and photophysical studies show that the light-induced MLCT excited state of the title complex is localized towards the potential diiron acceptor unit. However, the relatively mild potential required for the reduction of the acetylenic bipyridine together with the easily oxidized diiron portion leads to a reductive quenching of the excited state, instead. This process results in a transiently oxidized diiron unit which may explain the surprisingly high light sensitivity of complex 1.

Subject headings

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Keyword

mlct excited-states

photophysical properties

desulfovibrio-desulfuricans

complexes

coordination

ligand

delocalization

photochemistry

chemistry

evolution

Chemistry

Publication and Content Type

ref (subject category)

art (subject category)