Abstract
The structure of Ag 5 U(PS 4 ) 3 is unique, as in the literature there are no other structures of the type MAnPQ (M = transition metal, An = actinide, Q = S, Se, or Te). The compound has been synthesized at 1123 K by standard solid-state methods, and its single-crystal X-ray structure has been determined at 100(2) K. Ag 5 U(PS 4 ) 3 crystallizes in a remarkable new structure type in space group P3 2 21 of the trigonal system with three formula units in a hexagonal cell of dimensions a = b = 9.6635(2) Å, c = 17.1834(4) Å, and γ = 120°. In the structure, each U atom is coordinated to eight S atoms in a bicapped trigonal prismatic manner. Each P atom is tetrahedrally coordinated to four S atoms. Two of the three unique Ag atoms are connected to four S atoms in a distorted tetrahedral manner, whereas the third unique Ag atom forms an Ag 2 S 6 species. The overall structure consists of U polyhedra connected to each other via PS 4 tetrahedra through edge-sharing in a zigzag fashion along the c axis to form infinite layers. PS 4 groups and the Ag atoms pack these layers. From density functional theory calculations, the total density of states of Ag 5 U(PS 4 ) 3 is asymmetric with respect to spin and has finite spin polarization in the crystal cell: the magnetic moments of two of the U atoms are parallel, whereas the magnetic moment of the third U atom is antiparallel.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 535-539 |
| Number of pages | 5 |
| Journal | Inorganic chemistry |
| Volume | 58 |
| Issue number | 1 |
| DOIs | |
| State | Published - Jan 7 2019 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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Ag 5 U(PS 4 ) 3 : A Transition-Metal Actinide Phosphochalcogenide. / Mesbah, Adel; Prakash, Jai; Lebègue, Sébastien; Beard, Jessica C.; Malliakas, Christos D.; Ibers, James A.
In: Inorganic chemistry, Vol. 58, No. 1, 07.01.2019, p. 535-539.Research output: Contribution to journal › Article
TY - JOUR
T1 - Ag 5 U(PS 4 ) 3
T2 - A Transition-Metal Actinide Phosphochalcogenide
AU - Mesbah, Adel
AU - Prakash, Jai
AU - Lebègue, Sébastien
AU - Beard, Jessica C.
AU - Malliakas, Christos D.
AU - Ibers, James A.
PY - 2019/1/7
Y1 - 2019/1/7
N2 - The structure of Ag 5 U(PS 4 ) 3 is unique, as in the literature there are no other structures of the type MAnPQ (M = transition metal, An = actinide, Q = S, Se, or Te). The compound has been synthesized at 1123 K by standard solid-state methods, and its single-crystal X-ray structure has been determined at 100(2) K. Ag 5 U(PS 4 ) 3 crystallizes in a remarkable new structure type in space group P3 2 21 of the trigonal system with three formula units in a hexagonal cell of dimensions a = b = 9.6635(2) Å, c = 17.1834(4) Å, and γ = 120°. In the structure, each U atom is coordinated to eight S atoms in a bicapped trigonal prismatic manner. Each P atom is tetrahedrally coordinated to four S atoms. Two of the three unique Ag atoms are connected to four S atoms in a distorted tetrahedral manner, whereas the third unique Ag atom forms an Ag 2 S 6 species. The overall structure consists of U polyhedra connected to each other via PS 4 tetrahedra through edge-sharing in a zigzag fashion along the c axis to form infinite layers. PS 4 groups and the Ag atoms pack these layers. From density functional theory calculations, the total density of states of Ag 5 U(PS 4 ) 3 is asymmetric with respect to spin and has finite spin polarization in the crystal cell: the magnetic moments of two of the U atoms are parallel, whereas the magnetic moment of the third U atom is antiparallel.
AB - The structure of Ag 5 U(PS 4 ) 3 is unique, as in the literature there are no other structures of the type MAnPQ (M = transition metal, An = actinide, Q = S, Se, or Te). The compound has been synthesized at 1123 K by standard solid-state methods, and its single-crystal X-ray structure has been determined at 100(2) K. Ag 5 U(PS 4 ) 3 crystallizes in a remarkable new structure type in space group P3 2 21 of the trigonal system with three formula units in a hexagonal cell of dimensions a = b = 9.6635(2) Å, c = 17.1834(4) Å, and γ = 120°. In the structure, each U atom is coordinated to eight S atoms in a bicapped trigonal prismatic manner. Each P atom is tetrahedrally coordinated to four S atoms. Two of the three unique Ag atoms are connected to four S atoms in a distorted tetrahedral manner, whereas the third unique Ag atom forms an Ag 2 S 6 species. The overall structure consists of U polyhedra connected to each other via PS 4 tetrahedra through edge-sharing in a zigzag fashion along the c axis to form infinite layers. PS 4 groups and the Ag atoms pack these layers. From density functional theory calculations, the total density of states of Ag 5 U(PS 4 ) 3 is asymmetric with respect to spin and has finite spin polarization in the crystal cell: the magnetic moments of two of the U atoms are parallel, whereas the magnetic moment of the third U atom is antiparallel.
UR - http://www.scopus.com/inward/record.url?scp=85058576894&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85058576894&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b02739
DO - 10.1021/acs.inorgchem.8b02739
M3 - Article
C2 - 30525530
AN - SCOPUS:85058576894
VL - 58
SP - 535
EP - 539
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 1
ER -