Petel Brittney E, Brennessel William W, Matson Ellen M
Department of Chemistry , University of Rochester , Rochester , New York 14627 , United States.
J Am Chem Soc. 2018 Jul 11;140(27):8424-8428. doi: 10.1021/jacs.8b05298. Epub 2018 Jun 28.
We report the first example of oxygen-atom vacancy formation at the surface of a polyoxometalate, highlighting the ability of a polyoxovanadate-alkoxide cluster, [VO(OCH)], to function as a homogeneous model for reducible metal oxides. The removal of an oxide ion from [VO(OCH)] results in the formation of a reactive vanadium(III) cation within the multimetallic framework. Generation of [VO(OCH)] is confirmed by H NMR, infrared and electronic absorption spectroscopies, as well as electrospray ionization mass spectrometry. The consequences of oxygen atom removal on the electrochemical profile of the assembly are assessed, revealing that stabilization of the reduced cluster is achieved through delocalized electron density. The oxygen-atom vacancy permits activation of O, demonstrating the ability of polyoxovanadate-alkoxide clusters to serve as both structural and functional models of reducible metal oxides.
我们报道了在多金属氧酸盐表面形成氧原子空位的首个实例，突出了聚氧钒酸酯醇盐簇[VO(OCH)]作为可还原金属氧化物均相模型的功能。从[VO(OCH)]中去除一个氧离子会导致在多金属框架内形成一个具有反应活性的钒(III)阳离子。通过核磁共振氢谱、红外光谱、电子吸收光谱以及电喷雾电离质谱证实了[VO(OCH)]的生成。评估了去除氧原子对该组装体电化学曲线的影响，结果表明通过离域电子密度实现了还原簇的稳定化。氧原子空位使得O得以活化证明了聚氧钒酸酯醇盐簇作为可还原金属氧化物结构和功能模型的能力。
