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

Jin, Geng Bang; Malliakas, Christos D.; Lin, Jian

doi:10.1039/c7dt02145c

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

Journal Article · Thu Sep 28 00:00:00 EDT 2017 · Dalton Transactions

DOI:https://doi.org/10.1039/c7dt02145c· OSTI ID:1427545

Jin, Geng Bang ^[1]; Malliakas, Christos D. ^[2]; Lin, Jian ^[1]

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

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 P₂^4- 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-ThCu₂P₂ contains only P^3- 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 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-ThCu₂P₂ indicate a metal. These new compounds may be charge-balanced and formulated as Th⁴⁺Cu⁺(P₂^4-)_1/2P^3-, Th⁴⁺(Cu⁺)₂(P^3-)₂, and Th⁴⁺(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 UCuP₂ and UCu₂P₂ that were synthesized under similar experimental conditions, suggesting divergence of thorium-phosphide chemistry from uranium-phosphide chemistry.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Contributing Organization:: Northwestern University - International Institute for Nanotechnology (IIN)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1427545

Journal Information:: Dalton Transactions, Vol. 46; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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