Formed in 2009, the Archive Team (not to be confused with the archive.org Archive-It Team) is a rogue archivist collective dedicated to saving copies of rapidly dying or deleted websites for the sake of history and digital heritage. The group is 100% composed of volunteers and interested parties, and has expanded into a large amount of related projects for saving online and digital history.
- Article
- Published:
Structural and spectroscopic characterization of an einsteinium complex
- Korey P. Carter ORCID:orcid.org/0000-0003-4191-07401,
- Katherine M. Shield1,2,
- Kurt F. Smith1,
- Zachary R. Jones3,
- Jennifer N. Wacker3,4,
- Leticia Arnedo-Sanchez ORCID:orcid.org/0000-0001-6679-22801,
- Tracy M. Mattox ORCID:orcid.org/0000-0002-6520-830X5,
- Liane M. Moreau1,
- Karah E. Knope4,
- Stosh A. Kozimor ORCID:orcid.org/0000-0001-7387-05073,
- Corwin H. Booth ORCID:orcid.org/0000-0001-6827-00801 &
- Rebecca J. Abergel ORCID:orcid.org/0000-0002-3906-87611,2
Naturevolume 590, pages85–88(2021)Cite this article
Abstract
The transplutonium elements (atomic numbers 95–103) are a group of metals that lie at the edge of the periodic table. As a result, the patterns and trends used to predict and control the physics and chemistry for transition metals, main-group elements and lanthanides are less applicable to transplutonium elements. Furthermore, understanding the properties of these heavy elements has been restricted by their scarcity and radioactivity. This is especially true for einsteinium (Es), the heaviest element on the periodic table that can currently be generated in quantities sufficient to enable classical macroscale studies1. Here we characterize a coordination complex of einsteinium, using less than 200 nanograms of254Es (with half-life of 275.7(5) days), with an organic hydroxypyridinone-based chelating ligand. X-ray absorption spectroscopic and structural studies are used to determine the energy of the L3-edge and a bond distance of einsteinium. Photophysical measurements show antenna sensitization of EsIII luminescence; they also reveal a hypsochromic shift on metal complexation, which had not previously been observed in lower-atomic-number actinide elements. These findings are indicative of an intermediate spin–orbit coupling scheme in whichj–j coupling (whereby single-electron orbital angular momentum and spin are first coupled to form a total angular momentum,j) prevails over Russell–Saunders coupling. Together with previous actinide complexation studies2, our results highlight the need to continue studying the unusual behaviour of the actinide elements, especially those that are scarce and short-lived.
Access options
Subscribe to Journal
Get full journal access for 1 year
199,00 €
only 3,90 € per issue
All prices include VAT for Germany.
Rent or Buy article
Get time limited or full article access on ReadCube.
from$8.99
All prices are NET prices.
Data availability
All data are available in the paper. Additional details are available on request to the corresponding authors.
References
- 1.
Haire, R. G. inThe Chemistry of the Actinide and Transactinide Elements (eds Morss, L. R. et. al) 1577–1620 (Springer, 2011).
- 2.
Kelley, M. P. et al. Bond covalency and oxidation state of actinide ions complexed with therapeutic chelating agent 3,4,3-LI(1,2-HOPO).Inorg. Chem.57, 5352–5363 (2018).
- 3.
Hulet, E. K. Chemistry of the elements einsteinium through element-105.Radiochim. Acta32, 7–24 (1983).
- 4.
Pyykko, P. Relativistic effects in structural chemistry.Chem. Rev.88, 563–594 (1988).
- 5.
Ferguson, D. E. ORNL transuranium program: the production of transuranium elements.Nucl. Sci. Eng.17, 435–437 (1963).
- 6.
Meierfrankenfeld, D., Bury, A. & Thoennessen, M. Discovery of scandium, titanium, mercury, and einsteinium isotopes.At. Data Nucl. Data Tables97, 134–151 (2011).
- 7.
Thompson, S. G., Harvey, B. G., Choppin, G. R. & Seaborg, G. T. Chemical properties of elements 99 and 100.J. Am. Chem. Soc.76, 6229–6236 (1954).
- 8.
Choppin, G. R., Harvey, B. G. & Thompson, S. G. A new eluant for the separation of the actinide elements.J. Inorg. Nucl. Chem.2, 66–68 (1956).
- 9.
Horwitz, E. P., Bloomquist, C. A. A. & Henderson, D. J. The extraction chromatography of californium, einsteinium, and fermium with di(2-ethylhexyl)orthophosphoric acid.J. Inorg. Nucl. Chem.31, 1149–1166 (1969).
- 10.
Peterson, J. R. et al. Determination of the first ionization potential of einsteinium by resonance ionization mass spectroscopy (RIMS).J. Alloys Compd.271–273, 876–878 (1998).
- 11.
Haire, R. G. & Baybarz, R. D. Identification and analysis of einsteinium sesquioxide by electron diffraction.J. Inorg. Nucl. Chem.35, 489–496 (1973).
- 12.
Fellows, R. L., Peterson, J. R., Noé, M., Young, J. P. & Haire, R. G. X-ray diffraction and spectroscopic studies of crystalline einsteinium(III) bromide,253EsBr3.Inorg. Nucl. Chem. Lett.11, 737–742 (1975).
- 13.
Gutmacher, R. G., Evans, J. E. & Hulet, E. K. Sensitive spark lines of einsteinium.J. Opt. Soc. Am.57, 1389–1390 (1967).
- 14.
Nugent, L. J., Baybarz, R. D., Werner, G. K. & Friedman, H. A. Intramolecular energy transfer and sensitized luminescence in an einsteinium β-diketone chelate and the lower lying electronic energy levels of Es(III).Chem. Phys. Lett.7, 179–182 (1970).
- 15.
Harmon, H. D., Peterson, J. R. & McDowell, W. J. The stability constants of the monochloro complexes of Bk(III) and Es(III).Inorg. Nucl. Chem. Lett.8, 57–63 (1972).
- 16.
Harmon, H. D., Peterson, J. R., McDowell, W. J. & Coleman, C. F. The tetrad effect: the thiocyanate complex stability constants of some trivalent actinides.J. Inorg. Nucl. Chem.34, 1381–1397 (1972).
- 17.
McDowell, W. J. & Coleman, C. F. The sulfate complexes of some trivalent transplutonium actinides and europium.J. Inorg. Nucl. Chem.34, 2837–2850 (1972).
- 18.
Kelley, M. P. et al. Revisiting complexation thermodynamics of transplutonium elements up to einsteinium.Chem. Commun.54, 10578–10581 (2018).
- 19.
Bearden, J. A. & Burr, A. F. Reevaluation of X-ray atomic energy levels.Rev. Mod. Phys.39, 125–142 (1967).
- 20.
Daumann, L. J. et al. New insights into structure and luminescence of EuIII and SmIII complexes of the 3,4,3-LI(1,2-HOPO) ligand.J. Am. Chem. Soc.137, 2816–2819 (2015).
- 21.
Carnall, W. T., Cohen, D., Fields, P. R., Sjoblom, R. K. & Barnes, R. F. Electronic energy level and intensity correlations in the spectra of the trivalent actinide aquo ions. I. Es3+.J. Chem. Phys.59, 1785–1789 (1973).
- 22.
Beitz, J. V., Wester, D. W. & Williams, C. W. 5f state interaction with inner coordination sphere ligands: Es3+ ion fluorescence in aqueous and organic phases.J. Less Common Met.93, 331–338 (1983).
- 23.
Barbanel, A. Nephelauxetic effect and hypersensitivity in the optical spectra of actinides.Radiochim. Acta78, 91–95 (1997).
- 24.
Edelstein, N. M., Klenze, R., Fanghänel, T. & Hubert, S. Optical properties of Cm(III) in crystals and solutions and their application to Cm(III) speciation.Coord. Chem. Rev.250, 948–973 (2006).
- 25.
Moore, K. T. et al. Failure of Russell-Saunders coupling in the 5f states of plutonium.Phys. Rev. Lett.90, 196404 (2003).
- 26.
Lundberg, D. & Persson, I. The size of actinoid(III) ions – structural analysis vs. common misinterpretations.Coord. Chem. Rev.318, 131–134 (2016).
- 27.
Sturzbecher-Hoehne, M., Yang, P., D’Aleo, A. & Abergel, R. J. Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions.Dalton Trans.45, 9912–9919 (2016).
- 28.
Booth, C. H. & Hu, Y.-J. Confirmation of standard error analysis techniques applied to EXAFS using simulations.J. Phys. Conf. Ser.190, 012028 (2009).
- 29.
Abergel, R. J. et al. Biomimetic actinide chelators: an update on the preclinical development of the orally active hydroxypyridonate decorporation agents 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO).Health Phys.99, 401–407 (2010).
- 30.
Booth, C. H.RSXAP Analysis Package (Berkeley, 2016).
- 31.
Li, G. G., Bridges, F. & Booth, C. H. X-ray-absorption fine-structure standards: a comparison of experiment and theory.Phys. Rev. B52, 6332–6348 (1995).
- 32.
Ankudinov, A. L., Ravel, B., Rehr, J. J. & Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure.Phys. Rev. B58, 7565–7576 (1998).
- 33.
Rehr, J. J., Kas, J. J., Vila, F. D., Prange, M. P. & Jorissen, K. Parameter-free calculations of X-ray spectra with FEFF9.Phys. Chem. Chem. Phys.12, 5503–5513 (2010).
- 34.
Ahmad, I., Kondev, F. G., Koenig, Z. M., McHarris, W. C. & Yates, S. W. Two-quasiparticle states in250Bk studied by decay scheme and transfer reaction spectroscopy.Phys. Rev. C77, 054302 (2008).
Acknowledgements
254Es was supplied by the Isotope Program within the US Department of Energy (DOE), Office of Science, Office of Nuclear Physics. We thank N. Edelstein for discussions, M. Fox for γ spectrometer calibration, and N. Singh, B. Fairchild, S. Hays and R. Davis for assistance in planning and implementing experiments at the Stanford Synchrotron Radiation Lightsource (SSRL) and at the Molecular Foundry. This work was supported by the DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division at Lawrence Berkeley National Laboratory, under contract number DE-AC02-05CH1123, and at Los Alamos National Laboratory (LANL), an affirmative-action/equal-opportunity employer, managed by Triad National Security, LLC, for the NNSA of the DOE (contract number 89233218CNA000001). K.M.S. acknowledges support from a DOE Integrated University Program graduate research fellowship. Z.R.J. was supported by the Glenn T. Seaborg Institute at LANL. K.E.K. and J.N.W. were supported by the DOE, Office of Science, Office of Basic Energy Sciences, Early Career Research Program under award DE-SC0019190. J.N.W. was also supported by the DOE, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program, which is administered by the Oak Ridge Institute for Science and Education (ORISE) and managed by ORAU (contract number DE-SC0014664) for the DOE. Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the DOE, Office of Science, Office of Basic Energy Sciences under contract number DE-AC02-76SF00515. Near-infrared luminescence spectra were collected at the Molecular Foundry, a User Facility supported by the DOE, Office of Science, Office of Basic Energy Sciences under contract number DE-AC02-05CH1123.
Author information
Affiliations
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Korey P. Carter, Katherine M. Shield, Kurt F. Smith, Leticia Arnedo-Sanchez, Liane M. Moreau, Corwin H. Booth & Rebecca J. Abergel
Department of Nuclear Engineering, University of California, Berkeley, CA, USA
Katherine M. Shield & Rebecca J. Abergel
Los Alamos National Laboratory, Los Alamos, NM, USA
Zachary R. Jones, Jennifer N. Wacker & Stosh A. Kozimor
Department of Chemistry, Georgetown University, Washington, DC, USA
Jennifer N. Wacker & Karah E. Knope
Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Tracy M. Mattox
- Korey P. Carter
You can also search for this author inPubMed Google Scholar
- Katherine M. Shield
You can also search for this author inPubMed Google Scholar
- Kurt F. Smith
You can also search for this author inPubMed Google Scholar
- Zachary R. Jones
You can also search for this author inPubMed Google Scholar
- Jennifer N. Wacker
You can also search for this author inPubMed Google Scholar
- Leticia Arnedo-Sanchez
You can also search for this author inPubMed Google Scholar
- Tracy M. Mattox
You can also search for this author inPubMed Google Scholar
- Liane M. Moreau
You can also search for this author inPubMed Google Scholar
- Karah E. Knope
You can also search for this author inPubMed Google Scholar
- Stosh A. Kozimor
You can also search for this author inPubMed Google Scholar
- Corwin H. Booth
You can also search for this author inPubMed Google Scholar
- Rebecca J. Abergel
You can also search for this author inPubMed Google Scholar
Contributions
K.P.C., K.M.S., S.A.K. and R.J.A. conceived the study and designed the experiments. K.P.C., K.M.S. and S.A.K. prepared the XAS sample. S.A.K., Z.R.J. and J.N.W. collected XAS data. K.F.S., L.M.M. and C.H.B. analysed XAS results. K.P.C. and K.M.S. prepared the photoluminescence sample. L.A.-S., K.P.C. and T.M.M. collected luminescence data and interpreted the results. All authors discussed the experimental results and contributed to the manuscript.
Corresponding authors
Correspondence toStosh A. Kozimor orCorwin H. Booth orRebecca J. Abergel.
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review informationNature thanks Louise Natrajan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Fig. 1 Comparison of XANES data for [AnIII(HOPO)]− complexes.
AmIII, CmIII and CfIII spectra were reported previously2 and are compared to the EsIII data reported here, when plotted as a function of ΔE, the difference between the photon energyE and the peak in the first derivative of the dataE0.
Extended Data Fig. 2 Raw EXAFS data for [EsIII(HOPO)]−.
Data are shown as in Fig.2b, but extended beyond the range used in the fit. The data show the effect of a wide monochromator glitch near 7 Å−1 that limited the data range.
Extended Data Fig. 3 M–O bond distanceR versuskmax for [MIII(HOPO)]− actinide complexes.
These [MIII(HOPO)]− actinide complexes were characterized previously via EXAFS spectroscopy2. Note the difference in the fit model from ref.2 (Methods). The worsening of the fits below 6.5 Å−1 is at least partially related to the loss of fit degrees of freedom. For instance, the number of degrees of freedom decreases from 3.3 to 1.2 fromkmax = 6.5 Å−1 tokmax = 5.5 Å−1. The data for AmIII and CmIII are of higher quality because there was more material available. Samples masses are 27.1 μg, 10.9 μg and 3.3 μg for AmIII, CmIII and CfIII data, respectively. Reported one-standard-deviation errors are obtained from a previously described profiling method28.
Extended Data Fig. 4 Comparison of the first eight Es L3-edge XANES scans collected for [EsIII(HOPO)]− at 77 K.
The oldest scan is shown at the top and the newest at the bottom, as indicated by the black arrow. Each scan required about 40 min. Scans are offset for clarity.
Extended Data Fig. 5 Comparison of the averaged Es L3-edge XANES scans collected for [EsIII(HOPO)]− at 77 K.
The oldest averaged scan is shown at the top and the newest at the bottom, as indicated by the black arrow. Each averaged scan is taken from 10 individual scans and represents nearly 4 h of data acquisition time. Scans are offset for clarity.
Extended Data Fig. 6 Normalized excitation spectrum of [EsIII(HOPO)]− in aqueous solution.
Spectrum collected on monitoring at EsIII emission maximum (1,005 nm).
Extended Data Fig. 7 Schematics of the 3D-printed sample holder used for XAS measurements.
a,b, Top views of the sample holder.c, Computer-aided design (CAD) file for the sample holder.
Extended Data Fig. 8 Comparison of backscattering line shapes and phases for calculated [AnIII(HOPO)]− complexes.
Backscattering line shapes and phases were calculated using FEFF9.633 (Methods). The line shapes of the An–O pairs are shown for FEFF9.6 calculations using the same structure and varying only the An species to demonstrate the lack of change with species. These amplitudes are notk3-weighted, as in Fig.2 and Extended Data Fig.2, so there is no decrease above 4 Å−1 in the line shapes used for fitting, but rather a change in slope.
Extended Data Fig. 9 Comparison of calculated XANES spectra for [AnIII(HOPO)]− complexes.
Spectra were generated from FEFF9.6 calculations using a self-consistent field cluster of 6 Å and a full-multiple scattering cluster of 4 Å. Calculations on actinides generally overestimate the amount of 5f charge transfer when included in the valence orbitals, so these orbitals are treated as core orbitals here. The core–hole lifetime broadening used by the code increases from 8.7 eV to 10.3 eV from PuIII to EsIII, the effect of which is visible in the increased broadening of the spectra.
Extended Data Fig. 10 Comparison of local density of states (LDOS) for thed orbitals.
The LDOS is determined from the calculations in Extended Data Fig.9. The spectra are plotted as a function of ΔE, the difference between the photon energyE and the vacuum energy as calculated by FEFF9.6. The Fermi energy in all these calculations is about −7.6 eV, above which the states are unoccupied and therefore accessible to XANES. The calculations clearly show the 6d splitting between −5 eV and 0 eV. The splitting decreases by about 0.6 eV from PuIII to EsIII, in contrast to the increase in core–hole lifetime broadening. These effects are washed out in the final calculation in Extended Data Fig.9 by the much larger core–hole lifetime broadening.
Supplementary information
Rights and permissions
About this article
Cite this article
Carter, K.P., Shield, K.M., Smith, K.F.et al. Structural and spectroscopic characterization of an einsteinium complex.Nature590,85–88 (2021). https://doi.org/10.1038/s41586-020-03179-3
Comments
By submitting a comment you agree to abide by ourTerms andCommunity Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
