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Issue 1, 2017
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Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands

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Abstract

A new photoresponsive molecular polyanion in which two Fe(III) ions are simultaneously coordinated by two [A-α-PW9O34]9− polyoxometalate units and two oxalato ligands has been obtained. When irradiated with UV light its potassium salt, 1, exhibits a remarkable photocoloration effect, attributable to the partial reduction of the POM units to give rise to a mixed-valence species. The photoinduced process is intramolecular and involves electron transfer from the oxalato ligands, which partially decompose releasing CO2, towards the Fe(III) and the POM. This mechanism has been confirmed by DRS, IR, XPS and Mössbauer spectroscopy, magnetism and elemental analysis. An analogous derivative of 1 containing malonato ligands does not exhibit such photoactive behaviour, which is evidence that the oxalate ligand is essential for the photoactivity of 1. To our knowledge, 1 represents the first POM-based compound in which the photocoloration effect does not require the presence of intermolecular short interactions.

Graphical abstract: Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands

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Publication details

The article was received on 02 May 2016, accepted on 15 Aug 2016 and first published on 16 Aug 2016


Article type: Edge Article
DOI: 10.1039/C6SC01919F
Citation: Chem. Sci., 2017,8, 305-315
  • Open access: Creative Commons BY-NC license
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    Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands

    Y. Duan, J. C. Waerenborgh, J. M. Clemente-Juan, C. Giménez-Saiz and E. Coronado, Chem. Sci., 2017, 8, 305
    DOI: 10.1039/C6SC01919F

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