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Title: Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues

To explore the chemical analogy between thorium and heavier actinides in soft anionic environments, three new thorium phosphides (ThCuP 2, beta-ThCu 2P 2, and ThCu 5P 3) have been prepared through solid-state reactions using CuI as a reaction promoter. The structure of ThCuP 2 can be described as a filled UTe 2-type with both dimeric P 2 4- and monomeric P 3- 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-ThCu 2P 2 contains only P 3- anions and is isostructural with BaCu 2S 2. In this structure, Th is coordinated by seven P atoms in monocapped trigonal prismatic geometry and Cu is tetrahedrally coordinated by four P atoms. ThCu 5P 3 adopts the YCo 5P 3-type structure consisting of P 3- 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-ThCu 2P 2 indicate a metal. These new compounds may be charge-balanced and formulated as Th 4+Cumore » +(P 2 4-) 1/2P 3-, Th 4+(Cu +) 2(P 3-) 2, and Th 4+(Cu +) 5(P 3-) 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 UCuP 2 and UCu 2P 2 that were synthesized under similar experimental conditions, suggesting divergence of thorium-phosphide chemistry from uranium-phosphide chemistry.« less
Authors:
 [1] ;  [2] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Contributing Orgs:
Northwestern University - International Institute for Nanotechnology (IIN)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1427545

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., 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. doi:10.1039/c7dt02145c.
Jin, Geng Bang, Malliakas, Christos D., and Lin, Jian. 2017. "Thorium Copper Phosphides: More Diverse Metal-Phosphorus and Phosphorus-Phosphorus Interactions than U analogues". United States. doi: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 = {2017},
month = {9}
}

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