Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues
Abstract
To explore the chemical analogy between thorium and heavier actinides in soft anionic environments, three new thorium phosphides (ThCuP2, beta-ThCu2P2, and ThCu5P3) have been prepared through solid-state reactions using CuI as a reaction promoter. The structure of ThCuP2 can be described as a filled UTe2-type with both dimeric P24- and monomeric P3- anions, in which Th is coordinated by eight P atoms in a bicapped trigonal prismatic arrangement and Cu is tetrahedrally coordinated by four P atoms. β-ThCu2P2 contains only P3- anions and is isostructural with BaCu2S2. In this structure, Th is coordinated by seven P atoms in monocapped trigonal prismatic geometry and Cu is tetrahedrally coordinated by four P atoms. ThCu5P3 adopts the YCo5P3-type structure consisting of P3- anions. This structure contains Th atoms coordinated by six P atoms in a trigonal prismatic arrangement and Cu atoms that are either tetrahedrally coordinated by four P atoms or square pyramidally coordinated by five P atoms. Electric resistivity measurements and electronic structure calculations on β-ThCu2P2 indicate a metal. These new compounds may be charge-balanced and formulated as Th4+Cu+(P24-)1/2P3-, Th4+(Cu+)2(P3-)2, and Th4+(Cu+)5(P3-)3, respectively. The structural, bonding, and property relationships between these Th compounds and related actinide and rare-earth phases are discussed. Inmore »
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Contributing Org.:
- Northwestern University - International Institute for Nanotechnology (IIN)
- OSTI Identifier:
- 1427545
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 46; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jin, Geng Bang, Malliakas, Christos D., and Lin, Jian. Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues. United States: N. p., 2017.
Web. doi:10.1039/c7dt02145c.
Jin, Geng Bang, Malliakas, Christos D., & Lin, Jian. Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues. United States. https://doi.org/10.1039/c7dt02145c
Jin, Geng Bang, Malliakas, Christos D., and Lin, Jian. Thu .
"Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues". United States. https://doi.org/10.1039/c7dt02145c. https://www.osti.gov/servlets/purl/1427545.
@article{osti_1427545,
title = {Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues},
author = {Jin, Geng Bang and Malliakas, Christos D. and Lin, Jian},
abstractNote = {To explore the chemical analogy between thorium and heavier actinides in soft anionic environments, three new thorium phosphides (ThCuP2, beta-ThCu2P2, and ThCu5P3) have been prepared through solid-state reactions using CuI as a reaction promoter. The structure of ThCuP2 can be described as a filled UTe2-type with both dimeric P24- and monomeric P3- anions, in which Th is coordinated by eight P atoms in a bicapped trigonal prismatic arrangement and Cu is tetrahedrally coordinated by four P atoms. β-ThCu2P2 contains only P3- anions and is isostructural with BaCu2S2. In this structure, Th is coordinated by seven P atoms in monocapped trigonal prismatic geometry and Cu is tetrahedrally coordinated by four P atoms. ThCu5P3 adopts the YCo5P3-type structure consisting of P3- anions. This structure contains Th atoms coordinated by six P atoms in a trigonal prismatic arrangement and Cu atoms that are either tetrahedrally coordinated by four P atoms or square pyramidally coordinated by five P atoms. Electric resistivity measurements and electronic structure calculations on β-ThCu2P2 indicate a metal. These new compounds may be charge-balanced and formulated as Th4+Cu+(P24-)1/2P3-, Th4+(Cu+)2(P3-)2, and Th4+(Cu+)5(P3-)3, respectively. The structural, bonding, and property relationships between these Th compounds and related actinide and rare-earth phases are discussed. In conclusion, titled compounds display more diverse ion-ion interactions and different electronic structures from those in UCuP2 and UCu2P2 that were synthesized under similar experimental conditions, suggesting divergence of thorium-phosphide chemistry from uranium-phosphide chemistry.},
doi = {10.1039/c7dt02145c},
journal = {Dalton Transactions},
number = ,
volume = 46,
place = {United States},
year = {Thu Sep 28 00:00:00 EDT 2017},
month = {Thu Sep 28 00:00:00 EDT 2017}
}
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Distorted Phosphorus and Copper Square-Planar Layers in LaCu 1+ x P 2 and LaCu 4 P 3 : Synthesis, Crystal Structure, and Physical Properties
journal, October 2014
- Wang, Jian; Lee, Kathleen; Kovnir, Kirill
- Inorganic Chemistry, Vol. 54, Issue 3
Chains, planes, and antimonides
journal, November 2002
- Mills, A.
- Coordination Chemistry Reviews, Vol. 233-234
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Preparation and crystal structure of the actinoid ruthenium phosphides ThRu2P2 and URu2P2
journal, July 1992
- Glaum, R.; Albering, J. H.; Jeitschko, W.
- Journal of Alloys and Compounds, Vol. 185, Issue 2
A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe 3 } 2 ) 3 ] − (E = O, S, Se, Te)
journal, September 2012
- Brown, Jessie L.; Fortier, Skye; Lewis, Richard A.
- Journal of the American Chemical Society, Vol. 134, Issue 37
Atomic Radii and Interatomic Distances in Metals
journal, March 1947
- Pauling, Linus
- Journal of the American Chemical Society, Vol. 69, Issue 3
Ternary lanthanoid iron phosphides with YCo5P3 and Zr2Fe12P7-type structures
journal, December 1984
- Jeitschko, W.; Meisen, U.; Scholz, U. D.
- Journal of Solid State Chemistry, Vol. 55, Issue 3
Thorium heptaphosphide ThP7
journal, February 1986
- Von Schnering, Hans-Georg; Vu, Dong
- Journal of the Less Common Metals, Vol. 116, Issue 1
The Crystal Structures of Th4Fe17P10O1- and ThFe5P3
journal, June 1995
- Albering, Jörg H.; Jeitschko, Wolfgang
- Journal of Solid State Chemistry, Vol. 117, Issue 1
Covalency in f-element complexes
journal, January 2013
- Neidig, Michael L.; Clark, David L.; Martin, Richard L.
- Coordination Chemistry Reviews, Vol. 257, Issue 2
Actinoid transition metal phosphides An2T12P7 (An = Th, U; T = Fe, Co, Ni) and arsenides An2T12As7 (An = Th, U; T = Co, Ni) with Zr2Fe12P7 type structure
journal, January 2010
- Jeitschko, Wolfgang; Meisen, Ulrich; Albering, Jörg
- Dalton Transactions, Vol. 39, Issue 26
Synthesis, Properties, and Complex Crystal Structure of Th 2 Se 5
journal, December 2012
- Bellott, Brian J.; Malliakas, Christos D.; Koscielski, Lukasz A.
- Inorganic Chemistry, Vol. 52, Issue 2
Rare-Earth Manganese Copper Phosphides REMnCu 4 P 3 (RE = Gd–Ho): The First Quaternary Ordered Variants of the YCo 5 P 3 -Type Structure
journal, October 2014
- Ramachandran, Krishna K.; Stoyko, Stanislav S.; Mullen, C. Scott
- Inorganic Chemistry, Vol. 54, Issue 3
The Crystal Structure of Cu3P.
journal, January 1972
- Olofsson, Olle; Holmlund, Lars; Ingri, Nils
- Acta Chemica Scandinavica, Vol. 26
Crystal structure of UCu2P2
journal, February 1987
- Zolnierek, Z.; Noel, H.; Kaczorowski, D.
- Journal of the Less Common Metals, Vol. 128
Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes
journal, March 2014
- Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
- Angewandte Chemie International Edition, Vol. 53, Issue 17
Reinvestigation of Np 2 Se 5 : A Clear Divergence from Th 2 S 5 and Th 2 Se 5 in Chalcogen–Chalcogen and Metal–Chalcogen Interactions
journal, July 2013
- Jin, Geng Bang; Hu, Yung-Jin; Bellott, Brian
- Inorganic Chemistry, Vol. 52, Issue 15
Distortions from the Tetragonal HfCuSi 2 -Type Structures to the Orthorhombic GdCuAs 1.15 P 0.85 -Type Structures in REMX 2 ( RE = Rare Earth; M = Cu, Ag; X = P, As, Sb): Mismatch between the Sizes of the M and X Atoms
journal, September 2002
- Mozharivskyj, Yurij; Franzen, Hugo F.
- The Journal of Physical Chemistry B, Vol. 106, Issue 37
STRUCTURE TIDY – a computer program to standardize crystal structure data
journal, April 1987
- Gelato, L. M.; Parthé, E.
- Journal of Applied Crystallography, Vol. 20, Issue 2
Crystal Structure and Physical Properties of Uranium–Copper Oxyphosphide UCuPO
journal, July 2010
- Sakai, Hironori; Tateiwa, Naoyuki; D. Matsuda, Tatsuma
- Journal of the Physical Society of Japan, Vol. 79, Issue 7
Contributions to the Crystal Chemistry of Uranium Tellurides
journal, December 1996
- Stöwe, K.
- Journal of Solid State Chemistry, Vol. 127, Issue 2
Solid-state syntheses and single-crystal characterizations of three tetravalent thorium and uranium silicates
journal, January 2015
- Jin, Geng Bang; Soderholm, L.
- Journal of Solid State Chemistry, Vol. 221
Mineralization Routes to Polyphosphides: Cu 2 P 20 and Cu 5 InP 16
journal, June 2008
- Lange, Stefan; Bawohl, Melanie; Weihrich, Richard
- Angewandte Chemie International Edition, Vol. 47, Issue 30
Phase Diagrams and Thermodynamic Properties of the 70 Binary Alkali Halide Systems Having Common Ions
journal, July 1987
- Sangster, James; Pelton, Arthur D.
- Journal of Physical and Chemical Reference Data, Vol. 16, Issue 3
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
One-Dimensional [P 15 ] − Tubes in Layered Semiconducting AgP 15
journal, October 2015
- Grotz, Carolin; Schäfer, Konrad; Baumgartner, Maximilian
- Inorganic Chemistry, Vol. 54, Issue 22
Symmetry-Breaking Transitions from GdCuAs2 through GdCuAs1.15P0.85 to GdCuP2.20: Crystal Structure, Application of Landau Theory, Bonding, Magnetic and Electrical Properties
journal, November 2000
- Mozharivskyj, Yurij; Kaczorowski, Dariusz; Franzen, Hugo F.
- Journal of Solid State Chemistry, Vol. 155, Issue 1
Structure validation in chemical crystallography
journal, January 2009
- Spek, Anthony L.
- Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
Fully relativistic spin-polarized LMTO calculations of the magneto-optical Kerr effect of d and f ferromagnetic materials. III. Uranium chalcogenides and pnictides
journal, June 1999
- Antonov, V. N.; Harmon, B. N.; Yaresko, A. N.
- Physical Review B, Vol. 59, Issue 22
Anomalous magnetic and electricall behaviour of a complex phosphide U4Cu4P7
journal, July 1990
- Kaczorowski, D.; Troć, R.; Noël, H.
- Journal of the Less Common Metals, Vol. 161, Issue 2
Antiferromagnetic Structure of Uranium Diphosphide
journal, January 1966
- Troć, R.; Leciejewicz, J.; Ciszewski, R.
- physica status solidi (b), Vol. 15, Issue 2
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Dithorium undecaphosphide Th2P11, a polyphosphide with a one-dimensional superstructure generated by a periodic change in the covalent bonds
journal, December 1980
- Von Schnering, Hans-Georg; Wittmann, Manfred; Nesper, Reinhard
- Journal of the Less Common Metals, Vol. 76, Issue 1-2
Crystal growth and characterization of the transition-metal phosphides copper diphosphide, nickel diphosphide, and rhodium triphosphide
journal, February 1978
- Odile, J. P.; Soled, S.; Castro, C. A.
- Inorganic Chemistry, Vol. 17, Issue 2
Electronic structure and magneto-optical Kerr effect in the compound UCuP2
journal, July 2002
- Horpynyuk, O.; Nemoshkalenko, V. V.; Antonov, V. N.
- Low Temperature Physics, Vol. 28, Issue 7
Structural and magnetic properties of some new uranium ternary pnictides: UTX2 (T Fe, Co, Ni, Cu; X P, As, Sb, Bi)
journal, August 1992
- Kaczorowski, Dariusz
- Journal of Alloys and Compounds, Vol. 186, Issue 2
Thorium Oxo and Sulfido Metallocenes: Synthesis, Structure, Reactivity, and Computational Studies
journal, August 2011
- Ren, Wenshan; Zi, Guofu; Fang, De-Cai
- Journal of the American Chemical Society, Vol. 133, Issue 33
Nature of the states in actinide metals
journal, February 2009
- Moore, Kevin T.; van der Laan, Gerrit
- Reviews of Modern Physics, Vol. 81, Issue 1
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Electronic states in thorium under pressure
journal, February 1980
- Skriver, H. L.; Jan, J. -P.
- Physical Review B, Vol. 21, Issue 4
Au 3 SnP 7 @Black Phosphorus: An Easy Access to Black Phosphorus
journal, May 2007
- Lange, Stefan; Schmidt, Peer; Nilges, Tom
- Inorganic Chemistry, Vol. 46, Issue 10
UPTe, ThPTe and U 2 PTe 2 O: Actinide Pnictide Chalcogenides with Diphosphide Anions : Actinide Pnictide Chalcogenides with Diphosphide Anions
journal, January 2015
- Stolze, Karoline; Isaeva, Anna; Schwarz, Ulrich
- European Journal of Inorganic Chemistry, Vol. 2015, Issue 5
Chemistry and structural chemistry of phosphides and polyphosphides. 48. Bridging chasms with polyphosphides
journal, January 1988
- Von Schnering, Hans Georg; Hoenle, Wolfgang
- Chemical Reviews, Vol. 88, Issue 1
Extended Huckel tight-binding calculations of the electronic structure of and
journal, September 2003
- Galván, Donald H.; Dilley, N. R.; Maple, M. B.
- Physical Review B, Vol. 68, Issue 11
New ternary thorium and uranium compounds MYX
journal, October 1968
- Hulliger, F.
- Journal of the Less Common Metals, Vol. 16, Issue 2
Kristallstrukturen von Thoriumphosphiden
journal, March 1939
- Meisel, Karl
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 240, Issue 4
The crystal structures of thorium arsenides
journal, June 1955
- Ferro, R.
- Acta Crystallographica, Vol. 8, Issue 6
Preparation and crystal structure of YCo5P3 and isotypic lanthanoid cobalt phosphides
journal, September 1984
- Meisen, U.; Jeitschko, W.
- Journal of the Less Common Metals, Vol. 102, Issue 1
Triamidoamine uranium(IV)–arsenic complexes containing one-, two- and threefold U–As bonding interactions
journal, June 2015
- Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
- Nature Chemistry, Vol. 7, Issue 7
The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium( iv ) and uranium( iv ) alkyls
journal, January 2014
- Gardner, Benedict M.; Cleaves, Peter A.; Kefalidis, Christos E.
- Chem. Sci., Vol. 5, Issue 6
Crystal chemistry and electronic structure of actinide compounds
journal, September 1981
- Damien, D.; de Novion, C. H.
- Journal of Nuclear Materials, Vol. 100, Issue 1-3
Structural data of the actinide elements and of their binary compounds with non-metallic elements
journal, February 1987
- Benedict, Ulrich
- Journal of the Less Common Metals, Vol. 128
Preparation of the monophosphides and monochalcogenides of uranium and thorium by the volatile metal process
journal, June 1971
- Lovell, G. H. B.; Perels, D. R.; Britz, E. J.
- Journal of Nuclear Materials, Vol. 39, Issue 3
Structural chemistry of Ba2CdS3, Ba2CdSe3, BaCdS2, BaCu2S2 and BaCu2Se2
journal, January 1974
- Iglesias, J. E.; Pachali, K. E.; Steinfink, H.
- Journal of Solid State Chemistry, Vol. 9, Issue 1
Preparation and crystal structure of UCuP2
journal, May 1987
- Noël, H.; Żołnierek, Z.; Kaczorowski, D.
- Journal of the Less Common Metals, Vol. 132, Issue 2
Hypervalent Bonding in One, Two, and Three Dimensions: Extending the Zintl-Klemm Concept to Nonclassical Electron-Rich Networks
journal, July 2000
- A. Papoian, Garegin; Hoffmann, Roald
- Angewandte Chemie International Edition, Vol. 39, Issue 14
Critical behavior of specific heat and isothermal magnetocaloric coefficient in the ferromagnet
journal, December 2005
- Plackowski, T.; Kaczorowski, D.
- Physical Review B, Vol. 72, Issue 22