Identification of seven-coordinate LnIII ions in a LnIII[15-MCFe III N(shi)-5](OAc)2Cl species crystallized from methanol and pyridine

Elizabeth S Biros; Cassandra L Ward; Matthew J Allen; Jacob C Lutter

doi:10.1007/s10870-021-00900-6

Identification of seven-coordinate Ln^III ions in a Ln^III[15-MC_Fe ^III _N(shi)-5](OAc)₂Cl species crystallized from methanol and pyridine

J Chem Crystallogr. 2022 Jun;52(2):152-160. doi: 10.1007/s10870-021-00900-6. Epub 2021 Aug 21.

Authors

Elizabeth S Biros¹, Cassandra L Ward², Matthew J Allen¹, Jacob C Lutter¹

Affiliations

¹ Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI, 48202, USA.
² Lumingen Instrument Center, Wayne State University, 5101 Cass Avenue, Detroit, MI. 48202, USA.

Abstract

The title metallacrown (MC) complexes Ln^III[15-MC_Fe^IIIN(shi)-5](OAc)₂CI(C₅H₅N)₆ (Ln1), where OAc^- is acetate, shi^3- is salicylhydroximate, and Ln = Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns.

Keywords: Iron; Lanthanides; Metallacrown; Self-assembly; Seven-coordinate complexes.

Grants and funding

R01 EB027103/EB/NIBIB NIH HHS/United States