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Identification of Seven-coordinate LnIII Ions in a LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl Species Crystallized from Methanol and Pyridine

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Abstract

The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3− 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.

Graphic Abstract

The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3− is salicylhydroximate, and Ln = Gd and Dy, contains seven-coordinate capped octahedron geometries for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species.

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Data Availability

Single-crystal diffraction data are available in CIF format free of charge at www.ccdc.cam.ac.uk using deposition numbers 2083355 and 2083356.

Code Availability

Not applicable.

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Acknowledgements

JCL was partially supported by Wayne State University, and MJA gratefully acknowledges the National Institutes of Health (EB027103)

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Authors and Affiliations

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

    Elizabeth S. Biros, Matthew J. Allen & Jacob C. Lutter

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

    Cassandra L. Ward

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Contributions

EB synthesized the complexes; CLW collected single-crystal X-ray diffraction data and offered advice for HKLF5 refinement; MJA contributed to the manuscript draft; and JCL solved and refined diffraction data, interpreted characterization data, and drafted the manuscript.

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Correspondence to Jacob C. Lutter.

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Biros, E.S., Ward, C.L., Allen, M.J. et al. Identification of Seven-coordinate LnIII Ions in a LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl Species Crystallized from Methanol and Pyridine. J Chem Crystallogr 52, 152–160 (2022). https://doi.org/10.1007/s10870-021-00900-6

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