From +I to +IV, Alkalis to Actinides: Capturing Cations across the Periodic Table with Keggin Polyoxometalate Ligands.

Coordination chemistry trends across the periodic table are often difficult to probe experimentally due to limitations in finding a versatile but consistent chelating platform that can accommodate various elements without changing its coordination mode. Herein, we present new metal/ligand systems covering a wide range of ionic radii, charges, and elements. Five different ligands derived from the Keggin structure (HBW11O398-, PW11O397-, SiW11O398-, GeW11O398-, and GaW11O399-) were successfully crystallized with six different cations (Na+, Sr2+, Ba2+, La3+, Ce4+, and Th4+) and characterized by single-crystal X-ray diffraction. Twenty-five new compounds were obtained by using Cs+ as the counterion, yielding a consistent base formula of Csx[M(XW11O39)2]·nH2O. Despite having a similar first-coordination sphere geometry (i.e., 8-coordinated), the nature of the central cation was found to impact the long-range geometry of the complexes. This unique crystallographic data set shows that, despite the traditional consensus, the local geometry of the cation (i.e., metal-oxygen bond distance) is not enough to depict the full impact of the complexed metal ion. The bending and twisting of the complexes, as well as ligand-ligand distances, were all impacted by the nature of the central cation. We also observed that counterions play a critical role by stabilizing the geometry of the M(XW11)2 complex and directing complex-complex interactions in the lattice. We also define certain structural limits for this type of complex, with the large Ba2+ ion seemingly approaching those limits. This study thus lays the foundation for capturing the coordination chemistry of other rarer elements across the periodic table such as Ra2+, Ac3+, Bk4+, Cf3+, etc.

Crystal structure of hexa-chloro-thallate within a caesium chloride-phospho-tungstate lattice Cs9(TlCl6)(PW12O40)2·9CsCl.

Crystal formation of caesium thallium chloride phospho-tungstates, Cs9(TlCl6)(PW12O40)2·9CsCl showcases the ability to capture and crystallize octa-hedral complexes via the use of polyoxometalates (POMs). The large number of caesium chlorides allows for the POM [α-PW12O40]3- to arrange itself in a cubic close-packing lattice extended framework, in which the voids created enable the capture of the [TlCl6]3- complex.

Polyoxometalate Ligands Reveal Different Coordination Chemistries Among Lanthanides and Heavy Actinides.

Experimental studies involving actinide compounds are inherently limited in scope due to the radioactive nature of these elements and the scarcity and cost of their research isotopes. Now, ∼80 years after the introduction of the actinide concept by Glenn Seaborg, we still only have a limited understanding of the coordination chemistry of f-block metals when compared to more common elements such as the s-, p-, and d-blocks. This is particularly true for transplutonium actinides (Am, Cm, Bk, etc.) whose chemistry is often considered similar to trivalent lanthanides-mainly because of the lack of experimental data. We here report a metal-ligand system for which lanthanide and heavy actinide coordination compounds can be synthesized efficiently (i.e., requiring only a few micrograms) under identical conditions. Seventeen single crystal XRD structures of trivalent f-elements complexed to the polyoxometalate (POM) PW11O39 7- were obtained, including the full lanthanide series (Cs11Ln(PW11O39)2·nH2O, Ln = La to Lu, except Pm), the equivalent yttrium compound, a curium-POM compound (α2-Cs11Cm(PW11O39)2·33H2O), and the first two Am3+-POM compounds structurally characterized (α1-Cs11Am(PW11O39)2·6H2O and α2-Cs11Am(PW11O39)2·21H2O). Importantly, this represents a unique series of compounds built on the same 1:2 metal:ligand unit and where all the f-elements are 8-coordinated and squared antiprismatic, thus providing a consistent platform for intra- and inter-series comparison. Despite a similar first coordination sphere environment, significant crystallographic and spectroscopic differences were observed among early and late lanthanides, as well as lanthanides and actinides, and even between americium and curium. These results show that even within the same coordination chemistry framework, 4f and 5f elements exhibit fundamental chemical differences that cannot be explained by simple size-match arguments. This study offers a versatile coordination platform to magnify differences within the f-block that have remained difficult to observe with traditional ligand systems.

Synthesis and structural characterization of a hydrated sodium-caesium tetra-cosa-tungstate(VI), Na5Cs19[W24O84]·21H2O.

Crystal formation of penta-sodium nona-deca-cesium tetra-cosa-tungstate(VI) heneikosahydrate, Na5Cs19[W24O84]·21H2O, was successfully achieved by the conversion of [H2W12O42]10- through the addition of excess Cs+. The crystal structure comprising the toroidal isopolyoxidometalate is presented, as well as its Raman spectrum. Na5Cs19(H2O)21W24O84 crystallizes in the rhombohedral space group R with an obverse centering. The title compound represents the addition of a new member to the isopolytungstate family with mixed alkali counter-ions and contains rarely observed five-coordinate tungsten(VI) atoms in the [W24O84]24- anion (site symmetry C 3i ) arising from the conversion mediated by Cs+ counter-ions.

Characterization of the first Peacock-Weakley polyoxometalate containing a transplutonium element: curium bis-pentatungstate [Cm(W5O18)2]9.

Leveraging microgram-level techniques, we here present the first transplutonium bis-pentatungstate complex: NaCs8Cm(W5O18)2·14H2O (CmW5). Single crystal XRD, Raman, and fluorescence characterization show significant differences relative to analogous lanthanide compounds. The study reveals the unsuspected impact of counterions on fluorescence and vibrational modes of the curium complex and its lanthanide counterparts.