Speldrich, Manfred | Search NASA

DOE OSTI2021

Understanding the Stabilization and Tunability of Divalent Europium 2.2.2B Cryptates

Lanthanides such as europium with more accessible divalent states are useful for studying redox stability afforded by macrocyclic organic ligands. Substituted cryptands, such as 2.2.2B cryptand, that increase the oxidative stability of divalent europium also provide coordination environments that support synthetic alterations of Eu(II) cryptate complexes. Two single crystal structures were obtained containing nine-coordinate Eu(II) 2.2.2B cryptate complexes that differ by a single coordination site, the occupation of which is dictated by changes in reaction conditions. A crystal structure containing a [Eu(2.2.2B)Cl] + complex is obtained from a methanol–THF solvent mixture, while a methanol–acetonitrile solvent mixture affords a [Eu(2.2.2B)(CH 3 OH)] 2+ complex. While both crystals exhibit the typical blue emission observed in most Eu(II) containing compounds as a result of 4f 6 5d 1 to 4f 7 transitions, computational results show that the substitution of a Cl– anion in the place of a methanol molecule causes mixing of the 5d excited states in the Eu(II) 2.2.2B cryptate complex. Additionally, magnetism studies reveal the identity of the capping ligand in the Eu(II) 2.2.2B cryptate complex may also lead to exchange between Eu(II) metal centers facilitated by π-stacking interactions within the structure, slightly altering the anticipated magnetic moment. Finally, the synthetic control present in these systems makes them interesting candidates for studying less stable divalent lanthanides and the effects of precise modifications of the electronic structures of low valent lanthanide elements.

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DOE OSTI2020

Compression of curium pyrrolidine-dithiocarbamate enhances covalency

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell. This is even more pronounced in gadolinium, curium’s lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms. Therefore, the question arises of whether the frontier metal orbitals in curium(III)–ligand interactions can also be modified by applying pressure, and thus be induced to form metal–ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium–sulfur bonds in [Cm(pydtc) 4 ] – (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc) 4 ] – and of a Cm(III) mellitate that possesses only curium–oxygen bonds. Compared with the changes observed in the [Cm(pydtc) 4 ] – spectra, we observe smaller changes in the f–f transitions in the [Nd(pydtc) 4 ] – absorption spectrum and in the f–f emission spectrum of the Cm(III) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium–sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Furthermore, our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗