%0 Journal Article %A Izzet, G. %A Ishow, E. %A Delaire, J. %A Afonso, C. %A Tabet, J.-C. %A Proust, A. %D 2009 %T Photochemical Activation of an Azido Manganese-Monosubstituted Keggin Polyoxometalate: On the Road to a Mn(V)−Nitrido Derivative %U https://acs.figshare.com/articles/journal_contribution/Photochemical_Activation_of_an_Azido_Manganese_Monosubstituted_Keggin_Polyoxometalate_On_the_Road_to_a_Mn_V_Nitrido_Derivative/2805190 %R 10.1021/ic902046t.s001 %2 https://ndownloader.figshare.com/files/4499695 %K photolysi %K manganese %K 31 P NMR %K PW 11O %K IR %K Mn %K 2O %K UV %X The manganese(V)−nitrido polyoxometalate derivative [PW11O39{MnVN}]5− has been synthesized by photochemical activation of the parent manganese(III)−azido derivative [PW11O39MnIIIN3]5−. It was characterized by mass spectrometry, 31P NMR, UV−vis, and IR spectroscopies. An electrochemistry study indicated that only the Mn(V) state was stable. The photoactivation of the manganese(III)−azido derivative proceeds through two competitive routes, yielding to the targeted product of photooxidation {MnVN} or the undesirable product of photoreduction {MnIIL} (L = H2O, N3), depending on the photolysis conditions. A simplified photolysis mechanism involving two different excited states was proposed to account for the temperature and wavelength dependence. %I ACS Publications