This subproject is one of many research subprojects utilizing theresources provided by a Center grant funded by NIH/NCRR. The subproject andinvestigator (PI) may have received primary funding from another NIH source,and thus could be represented in other CRISP entries. The institution listed isfor the Center, which is not necessarily the institution for the investigator.Corroles are ring-contracted porphyrin analogues, which are believed to stabilize unusually high metal oxidation states. However, determination of oxidation state has generally been inferred by indirect methods, and there is some disagreement in the literature as to whether the oxidation has occurred on the metal center or on the corrole macrocycle. We propose metal K-edge x-ray absorption spectroscopy (XAS) to directly determine the oxidation state in a series of metal corrole complexes. Detailed analysis of the metal pre-edge region will provide information about the degree of metal 3d-4p mixing. These studies will be coupled with polarized single crystal XAS studies, which will allow for separation of the corrole in-plane and out-plane 4p mixing contributions, and may provide insight into the electronic structural contributions to high-valent metal ion stabilization.
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