A new iron–sulfur cluster compound, namely [(μ-BNT)Fe
2(CO)
6] (
; BNT = (
R)-1,1′-binaphthalene-2,2′-dithiol), was synthesized by self-assembly of BNT with [Fe
3(CO)
12] and characterized using
1H NMR,
13C NMR, infrared spectra and elemental analysis. The H
2 evolution activity of
was evaluated in a constructed homogeneous photocatalytic system by combining
as catalyst, xanthene dyes as photosensitizer and triethylamine as sacrificial reagent, to give efficient H
2 generation under visible-light irradiation (
λ > 420 nm). The maximum H
2 evolution of 404 turnovers (versus catalyst) was recorded under optimal conditions in CH
3CN–H
2O (1:1, v/v) after 4 h irradiation. The mechanism of H
2 evolution is briefly discussed using fluorescence spectra and electrochemical analysis. Copyright