Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Equipe Polyoxométallates Case courier 42, UPMC Univ Paris 06, 4 place Jussieu, 75252 Paris cedex 05, France.
Inorg Chem. 2009 Dec 21;48(24):11865-70. doi: 10.1021/ic902046t.
The manganese(V)-nitrido polyoxometalate derivative PW(11)O(39){Mn(V)N} has been synthesized by photochemical activation of the parent manganese(III)-azido derivative PW(11)O(39)Mn(III)N(3). It was characterized by mass spectrometry, (31)P 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 {Mn(V)N} or the undesirable product of photoreduction {Mn(II)L} (L = H(2)O, N(3)), depending on the photolysis conditions. A simplified photolysis mechanism involving two different excited states was proposed to account for the temperature and wavelength dependence.
锰(V)-亚硝基多金属氧酸盐衍生物PW(11)O(39){Mn(V)N}通过光化学激活母体锰(III)-叠氮衍生物PW(11)O(39)Mn(III)N(3)合成。它通过质谱、(31)P NMR、UV-vis 和 IR 光谱进行了表征。电化学研究表明只有 Mn(V)态是稳定的。锰(III)-叠氮衍生物的光激活通过两条竞争性途径进行，取决于光解条件，生成目标产物光氧化{Mn(V)N}或不期望的产物光还原{Mn(II)L}(L = H(2)O, N(3))。提出了一种简化的光解机制，涉及两个不同的激发态，以解释温度和波长的依赖性。
