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Issue 1, 2016
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Photoinduced electron transfer from the oxo–MoIVselenolato complex to oxygen

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Abstract

[NBu4][MoO(bpy)(mnt)(SePh)]·CH2Cl2 (1) and [NBu4][MoO(phen)(mnt)(SePh)]·CH2Cl2 (2) complexes; (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, mnt = maleonitriledithiolate ion) stabilized by aromatic diimine have been synthesized and characterized. These complexes under aerobic conditions on irradiation with sunlight (or with light from a tungsten lamp) in solution generate superoxide radicals concomitant to the formation of paramagnetic Mo(V) species due to a single electron transfer from the Mo(IV) complex to oxygen. The Mo(V) produced under photo-irradiation was characterized by EPR spectroscopy and the generated superoxide radical has been shown to transform nitrobluetetrazoleum (NBT) chloride to blue diformazan. Both 1 (and 2) are phosphorescent having an emission lifetime of 6–8 μs. Ground state and time dependent density functional theoretical calculations confirm that the electronic transitions from predominantly metal based molecular orbitals are responsible for the low-lying charge transfer excited states and also for the observed interaction with oxygen.

Graphical abstract: Photoinduced electron transfer from the oxo–MoIVselenolato complex to oxygen

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Publication details

The article was received on 16 Sep 2015, accepted on 09 Nov 2015 and first published on 12 Nov 2015


Article type: Paper
DOI: 10.1039/C5NJ02494C
Author version available: Download Author version (PDF)
Citation: New J. Chem., 2016,40, 626-633
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    Photoinduced electron transfer from the oxo–MoIVselenolato complex to oxygen

    J. Mitra and S. Sarkar, New J. Chem., 2016, 40, 626
    DOI: 10.1039/C5NJ02494C

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