Abstract

Lanthanide rare-earth metals are ubiquitous in modern technologies1–5, but we know little about chemistry of the 61st element, promethium (Pm)6, a lanthanide that is highly radioactive and inaccessible. Despite its importance7,8, Pm has been conspicuously absent from the experimental studies of lanthanides, impeding our full comprehension of the so-called lanthanide contraction phenomenon: a fundamental aspect of the periodic table that is quoted in general chemistry textbooks. Here we demonstrate a stable chelation of the 147Pm radionuclide (half-life of 2.62 years) in aqueous solution by the newly synthesized organic diglycolamide ligand. The resulting homoleptic PmIII complex is studied using synchrotron X-ray absorption spectroscopy and quantum chemical calculations to establish the coordination structure and a bond distance of promethium. These fundamental insights allow a complete structural investigation of a full set of isostructural lanthanide complexes, ultimately capturing the lanthanide contraction in solution solely on the basis of experimental observations. Our results show accelerated shortening of bonds at the beginning of the lanthanide series, which can be correlated to the separation trends shown by diglycolamides9–11. The characterization of the radioactive PmIII complex in an aqueous environment deepens our understanding of intra-lanthanide behaviour12–15 and the chemistry and separation of the f-block elements16.

Original languageEnglish
Pages (from-to)819-823
Number of pages5
JournalNature
Volume629
Issue number8013
DOIs
StatePublished - May 23 2024

Funding

This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division and Materials Sciences and Engineering Division under award number DE-SC00ERKCG21\u00A0(D.M.D., S.P., S.R.,\u00A0S.J.-P. and\u00A0A.S.I.);\u00A0the DOE Isotope Programme, managed by the Office of Science for Isotope R&D and Production\u00A0(F.D.W., R.T.M., L.H.D., S.K.C., T.D., A.M., M.S., S.M.V.,\u00A0S.M.D. and I.P.);\u00A0and\u00A0the DOE, Office of Science, Office of\u00A0Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division\u00A0under award number DE-SC00 ERKCC08\u00A0(J.D.E.). Use of the NSLS-II (NIST beamline 6-BM) was supported by the DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. This research used resources of the Oak Ridge Leadership Computing Facility (OLCF) and the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the DOE under contract no. DE-AC05-00OR22725. This research used the hot cells and glovebox laboratories and other resources of the Radiochemical Engineering Development Centre, a DOE Office of Science research facility operated by the Oak Ridge National Laboratory. D.M.D., B.R., I.P. and A.S.I. thank K. Wehunt of\u00A0Brookhaven National Laboratory for her help with handling radioactive samples at NSLS-II and E. Jahrman of\u00A0the National Institute of Standards and Technology for critically reading the manuscript and providing helpful suggestions. I.P. and A.S.I. thank R. Copping, L. Harvey, N. Sims and M. Du for helpful discussions. This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division and Materials Sciences and Engineering Division under award number DE-SC00ERKCG21 (D.M.D., S.P., S.R., S.J.-P. and A.S.I.); the DOE Isotope Programme, managed by the Office of Science for Isotope R&D and Production (F.D.W., R.T.M., L.H.D., S.K.C., T.D., A.M., M.S., S.M.V., S.M.D. and I.P.); and the DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division under award number DE-SC00 ERKCC08 (J.D.E.). Use of the NSLS-II (NIST beamline 6-BM) was supported by the DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. This research used resources of the Oak Ridge Leadership Computing Facility (OLCF) and the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the DOE under contract no. DE-AC05-00OR22725. This research used the hot cells and glovebox laboratories and other resources of the Radiochemical Engineering Development Centre, a DOE Office of Science research facility operated by the Oak Ridge National Laboratory. D.M.D., B.R., I.P. and A.S.I. thank K. Wehunt of Brookhaven National Laboratory for her help with handling radioactive samples at NSLS-II and E. Jahrman of the National Institute of Standards and Technology for critically reading the manuscript and providing helpful suggestions. I.P. and A.S.I. thank R. Copping, L. Harvey, N. Sims and M. Du for helpful discussions.

FundersFunder number
Basic Energy Sciences
Oak Ridge National Laboratory
U.S. Department of Energy
Office of Science for Isotope R&D and Production
Office of Science
Chemical Sciences, Geosciences, and Biosciences Division and Materials Sciences and Engineering DivisionDE-SC00ERKCG21
Chemical Sciences, Geosciences, and Biosciences DivisionDE-SC00 ERKCC08
Chemical Sciences, Geosciences, and Biosciences Division
Brookhaven National LaboratoryDE-SC0012704
Brookhaven National Laboratory
Compute and Data Environment for ScienceDE-AC05-00OR22725

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