CT interactions of the cuboidal cluster Fe4S4. Photoredox decomposition of (C5H5)4Fe4S4 |
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| Affiliation: | 1. School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074, China;2. Key Laboratory of Three Gorges Reservoir Region''s Eco-Environment, Ministry of Education, Chongqing University, Chongqing 400045, China;3. National Centre for International Research of Low-carbon and Green Buildings, Chongqing University, Chongqing 400045, China;4. T.Y. Lin International Engineering Consulting (China) Co., Ltd, Chongqing 401121, China |
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| Abstract: | The cluster complex (C5H5)4Fe4S4 formally contains Fe(III) and sulfide as constituents. In agreement with this assignment, the long-wavelength absorptions of the cluster are attributed to S2 − to Fe(III) LMCT transitions. In solutions of acetonitrile, LMCT excitation of the cluster complex leads to a photoredox decomposition yielding Fe(II) and elemental sulfur. Upon a one-electron oxidation of (C5H5)4Fe4S4, the cation (C5H5)4Fe4S4]+ is obtained, which is much more stable to water, air and light than the neutral parent cluster. Upon addition of M(CN)6]4 − with MRu and Os to aqueous solutions of this cation, dark blue and violet colors, respectively, immediately develop, which are attributed to outer-sphere CT absorptions of the ion pairs (C5H5)4Fe4S4]+/M(CN)6]4 −. |
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