Mixed transition metal oxides are central to the development of materials for oxygen evolution reaction, oxygen reduction reaction, and energy storage. Discreet clusters containing mixed transition metal-oxido moiety were targeted. A series of heterometallic trimanganese-tetraoxido cubanes (M'Mn3O4) supported by a trisalkoxy-hexapyridyl ligand with a 1,3,5-triarylbenzene spacer were previously reported where M' is a redox-inactive metal.  Transmetallation of the Ca2+ center of [CaMn3O4] with M2+ salts (M = Fe, Co, Ni, Cu) yielded the mixed transition metal manganese-oxido cubanes (MMn3O4). The series of complexes was characterized by single crystal X-ray diffraction, dispersive difference diffraction analysis, cyclic voltammetry, M�ssbauer spectroscopy, and X-ray absorption spectroscopy. Dispersive difference diffraction analysis confirmed that the Mn centers remain at their original sites within the cubane moiety upon transmetallation of the Ca by other metals. Cyclic voltammetry studies show significant changes in the MnIV3/MnIIIMnIV2 redox potentials as a function of metal M. Through M�ssbauer spectroscopy, XANES, and X-ray diffraction studies, it was determined that redox reactions occur at Mn centers instead of M. These well-defined complexes have been employed as precursors for heterogeneous water oxidation electrocatalysts.

Synthesis and characterization of a series of mixed transition metal oxido cubanes (MMnO<sub>4</sub>)

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Synthesis and characterization of a series of mixed transition metal oxido cubanes (MMnO4)

Synthesis and characterization of a series of mixed transition metal oxido cubanes (MMnO₄)