Thorium copper phosphides: more diverse metal-phosphorus and phosphorus-phosphorus interactions than U analogues
Jin, GB; Malliakas, CD; Lin, J
2017
发表期刊DALTON TRANSACTIONS
ISSN1477-9226
卷号46期号:36页码:12041-12052
文章类型期刊论文
摘要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 P-2(4-) 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. beta-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 beta-ThCu2P2 indicate a metal. These new compounds may be charge-balanced and formulated as Th4+Cu+(P-2(4-))(1/2)P3-, 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. 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.
关键词Crystal-structure Structural Chemistry Uranium Chalcogenides Electronic-structure Transport-properties Black Phosphorus Rare-earth Polyphosphides Complexes Pnictides
DOI10.1039/c7dt02145c
关键词[WOS]CRYSTAL-STRUCTURE ; STRUCTURAL CHEMISTRY ; URANIUM CHALCOGENIDES ; ELECTRONIC-STRUCTURE ; TRANSPORT-PROPERTIES ; BLACK PHOSPHORUS ; RARE-EARTH ; POLYPHOSPHIDES ; COMPLEXES ; PNICTIDES
收录类别SCI
语种英语
WOS记录号WOS:000411224500010
引用统计
文献类型期刊论文
条目标识符http://ir.sinap.ac.cn/handle/331007/28878
专题中科院上海应用物理研究所2011-2018年
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Jin, GB,Malliakas, CD,Lin, J. Thorium copper phosphides: more diverse metal-phosphorus and phosphorus-phosphorus interactions than U analogues[J]. DALTON TRANSACTIONS,2017,46(36):12041-12052.
APA Jin, GB,Malliakas, CD,&Lin, J.(2017).Thorium copper phosphides: more diverse metal-phosphorus and phosphorus-phosphorus interactions than U analogues.DALTON TRANSACTIONS,46(36),12041-12052.
MLA Jin, GB,et al."Thorium copper phosphides: more diverse metal-phosphorus and phosphorus-phosphorus interactions than U analogues".DALTON TRANSACTIONS 46.36(2017):12041-12052.
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