Jessica C. Beard

Three New Quaternary Actinide Chalcogenides Ba2TiUTe7, Ba2CrUTe7, and Ba2CrThTe7: Syntheses, Crystal Structures, Transport Properties, and Theoretical Studies

The three new quaternary actinide chalcogenides Ba2TiUTe7, Ba2CrUTe7, and Ba2CrThTe7 have been synthesized. From single-crystal X-ray diffraction studies these isostructural compounds are found to crystallize in a new structure type in space group D2h16–Pnma of the orthorhombic system. The structure features ∞1[MAnTe74–] strips (M = Cr or Ti; An = Th or U) that propagate in the b-direction and are separated by Ba cations. An atoms are coordinated to eight Te atoms in a bicapped trigonal-prismatic geometry while M atoms are octahedrally coordinated to six Te atoms. Sharing of the AnTe8 and MTe6 polyhedra forms ∞1[MAnTe74–] strips. The presence of the infinite linear Te–Te–Te chains in these compounds makes assignment of oxidation states arbitrary. Resistivity measurements and DFT calculations provide further insight into the properties of these compounds.

Positional flexibility: Syntheses and characterization of six uranium chalcogenides related to the 2H hexagonal perovskite family

Six new uranium chalcogenides, Ba4USe6, Ba3FeUSe6, Ba3MnUSe6, Ba3MnUS6, Ba3.3Rb0.7US6, and Ba3.2K0.8US6, related to the 2H hexagonal perovskite family have been synthesized by solid-state methods at 1173 K. These isostructural compounds crystallize in the K4CdCl6 structure type in space group D3d6–R3̅c of the trigonal system with six formula units per cell. This structure type is remarkably flexible. The structures of Ba3FeUSe6, Ba3MnUSe6, and Ba3MnUS6 consist of infinite ∞1[MUQ66–] chains (M = Fe or Mn; Q = S or Se) oriented along the c axis that are separated by Ba atoms. These chains are composed of alternating M-centered octahedra and U-centered trigonal prisms sharing triangular faces; in contrast, in the structures of Ba4USe6, Ba3.3Rb0.7US6, and Ba3.2K0.8US6, there are U-centered octahedra alternating with Ba-, Rb-, or K-centered trigonal prisms. Moreover, the Ba4USe6, Ba3FeUSe6, Ba3MnUSe6, and Ba3MnUS6 compounds contain U4+, whereas Ba3.3Rb0.7US6 and Ba3.2K0.8US6 are mixed U4+/5+ compounds. Resistivity and μ-Raman spectroscopic measurements and DFT calculations provide additional insight into these interesting subtle structural variations.

Syntheses, Crystal Structures, Optical and Theoretical Studies of the Actinide Thiophosphates SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2

Three new actinide thiophosphates, SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2, have been synthesized by high-temperature solid-state methods, and their crystal structures were determined from single-crystal X-ray diffraction studies. These three isostructural compounds crystallize in a new structure type in space group D4h13-P42/mbc of the tetragonal system. Their structure features infinite one-dimensional chains of ∞1[An(PS4)2(2–)] anions (An = U or Th). Each An atom is coordinated by eight S atoms in a bicapped trigonal prism, and each P atom is tetrahedrally bonded to four S atoms. The compounds are readily charge balanced as Ak2+An4+(P5+(S2–)4)2. Optical studies on single crystals of SrU(PS4)2 and BaU(PS4)2 as well as ground single crystals of SrTh(PS4)2 revealed a direct band gap of 2.13(2) eV and an indirect band gap value of 1.99(2) eV for SrU(PS4)2 and a direct and indirect gap of about 2.28(2) eV for BaU(PS4)2. SrTh(PS4)2 has a relatively large band gap of 3.02(2) eV. DFT calculations for SrU(PS4)2 and BaU(PS4)2 using the HSE functional predict both compounds to be antiferromagnetic and have very similar electronic structures with band gaps of 2.7 eV. The band gap calculated for SrTh(PS4)2 is 3.2 eV.

Four New Actinide Chalcogenides Ba2Cu4USe6, Ba2Cu2ThSe5, Ba2Cu2USe5, and Sr2Cu2US5: Crystal Structures and Physical Properties

Four new actinide chalcogenides—namely, Ba2Cu4USe6, Ba2Cu2ThSe5, Ba2Cu2USe5, and Sr2Cu2US5—were synthesized via solid-state methods at 1173 K. Single-crystal X-ray diffraction studies show that Ba2Cu4USe6 crystallizes in a new structure type in space group C2h5–P21/c of the monoclinic system, whereas the three other compounds are isostructural and adopt the Ba2Cu2US5 structure type in space group C2h3–C2/m, also of the monoclinic system. These Ak/Cu/An/Q structures (Ak = alkaline-earth metal; An = actinide; Q = chalcogen) have no short Q–Q interactions and, hence, are charge-balanced with Ak2+, Cu1+, An4+, and Q2–. Crystal structures of all these compounds are two-dimensional and feature layers that are separated by Ba2+ cations. The compositions of these layers differ. In the structure of Ba2Cu4USe6, the ∞2[Cu4USe64–] layers comprising USe6 octahedra and CuSe4 tetrahedra stack perpendicular to the a-axis. These ∞2[Cu4USe64–] layers show short Cu–Cu interactions. In the three isostructural Ak2Cu2AnQ5 compounds, AnQ6 octahedra and CuQ4 tetrahedra are connected along the c-axis in the sequence “...oct tet tet oct tet tet...” to form the ∞2[Cu2AnQ54–] layers. Resistivity, optical, and DFT calculations show semiconducting behavior for these compounds.

Two new ternary chalcogenides Ba2ZnQ3 (Q = Se, Te) with chains of ZnQ4 tetrahedra: syntheses, crystal structure, and optical and electronic properties

Abstract Single crystals of Ba2ZnQ3 (Q = Se, Te) were obtained by solid-state reactions at 1173 K. These isostructural compounds crystallize in the K2AgI3 structure type. The Zn atoms in this structure are coordinated to four Q atoms (2 Q1, 1 Q2, 1 Q3) and these form a distorted tetrahedron around each Zn atom. Each ZnQ4 tetrahedron shares two corners with neighboring ZnQ4 tetrahedra resulting in the formation of infinite chains of [ZnQ44−] units. The absorption spectrum of a single crystal of Ba2ZnTe3 shows an absorption edge at 2.10(2) eV, consistent with the dark-red color of the crystals. From DFT calculations Ba2ZnSe3 and Ba2ZnTe3 are found to be semiconductors with electronic band gaps of 2.6 and 1.9 eV, respectively.