Similar but Different: Structural and Spectroscopic Characterization of Series of Neodymium, Europium, Americium, and Curium Coordination Complexes

Series of curium, americium, europium, and neodymium complexes with five different polyoxometalate (POM) ligands were structurally and spectroscopically characterized: Na_<i>x</i>Cs_<i>y</i>H_<i>z</i>[M(XW₁₁O₃₉)₂]·<i>n</i>H₂O, where M = Nd³⁺, Eu³⁺, Am³⁺, or Cm³⁺ and X = B³⁺, Ga³⁺, Si⁴⁺, Ge⁴⁺, or P⁵⁺. This first "serial approach" on transplutonium chemistry was allowed by minimizing the amount of f-element needed per synthesis down to ∼10 μg. This offers a unique opportunity to contrast structural and spectroscopic properties of trivalent actinide with those of lanthanide compounds under identical conditions. The results showcase that although actinide(III) and lanthanide(III) can make isostructural complexes, their solid-state coordination chemistries deviate significantly. The curium and americium compounds were found to be more uniform than their europium and neodymium counterparts, respectively. The particular symmetry of the Cm-POMs also enables the observation of rarely seen emission bands, which hints at vibronic coupling or new emissive pathways. Additionally, the Cm-POM and Eu-POM complexes were characterized via steady-state and time-resolved excitation and emission spectroscopy in solutions containing five different counterions (Li⁺, Na⁺, K⁺, Rb⁺, or Cs⁺), representing 50 combinations of alkali/[M^III(XW₁₁)₂]^<i>n</i>- complexes. The Cm-POMs respond to the alkali counterions by improving symmetry from Li⁺ to Cs⁺, while the Eu-POMs do the opposite. The luminescence lifetimes of the Cm-POMs also depart from the ideal Kimura equation. This study provides a rare, and perhaps the most comprehensive, experimental data set comparing heavy actinides and lanthanides via single crystal XRD plus, solution-state, solid-state, and time-resolved emission spectroscopy and demonstrates that lanthanides are only a coarse approximation for actinide elements.