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J Am Chem Soc. 2018 Mar 28;140(12):4391-4400. doi: 10.1021/jacs.8b00465. Epub 2018 Mar 19.

Unique [Mn6Bi5]- Nanowires in KMn6Bi5: A Quasi-One-Dimensional Antiferromagnetic Metal.

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Department of Physics , Zhejiang University , Hangzhou 310027 , China.
Materials Science Division , Argonne National Laboratory , Argonne , Illinois 60439 , United States.
Department of Materials Science and Engineering , Northwestern University , Evanston , Illinois 60208 , United States.
Department of Chemistry , Zhejiang University , Hangzhou 310027 , China.
Department of Physics , Hangzhou Normal University , Hangzhou 310036 , China.
State Key Lab of Silicon Materials , Zhejiang University , Hangzhou 310027 , China.
Collaborative Innovation Centre of Advanced Microstructures , Nanjing University , Nanjing 210093 , China.
Department of Chemistry , Northwestern University , Evanston , Illinois 60208 , United States.


We report a new quasi-one-dimensional compound KMn6Bi5 composed of parallel nanowires crystallizing in a monoclinic space group C2/ m with a = 22.994(2) Å, b = 4.6128(3) Å, c = 13.3830(13) Å and β = 124.578(6)°. The nanowires are infinite [Mn6Bi5]- columns each of which is composed of a nanotube of Bi atoms acting as the cladding with a nanorod of Mn atoms located in the central axis of the nanotubes. The nanorods of Mn atoms inside the Bi cladding are stabilized by Mn-Mn bonding and are defined by distorted Mn-centered cluster icosahedra of Mn13 sharing their vertices along the b axis. The [Mn6Bi5]- nanowires are linked with weak internanowire Bi-Bi bonds and charge balanced with K+ ions. The [Mn6Bi5]- nanowires were directly imaged by high-resolution transmission electron microscopy and scanning transmission electron microscopy. Magnetic susceptibility studies show one-dimensional characteristics with an antiferromagnetic transition at ∼75 K and a small average effective magnetic moment (1.56 μB/Mn for H ∥ b and 1.37 μB/Mn for H ⊥ b) of Mn from Curie-Weiss fits above 150 K. Specific heat measurements reveal an electronic specific heat coefficient γ of 6.5(2) mJ K-2(mol-Mn)-1 and a small magnetic entropy change Δ Smag ≈ 1.6 J K-1 (mol-Mn)-1 across the antiferromagnetic transition. In contrast to a metallic resistivity along the column, the resistivity perpendicular to the column shows a change from a semiconducting behavior at high temperatures to a metallic one at low temperatures, indicating an incoherent-to-coherent crossover of the intercolumn tunneling of electrons.


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