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

Jin Ke Bao; Zhang Tu Tang; Hee Joon Jung; Ji Yong Liu; Yi Liu; Lin Li; Yu Ke Li; Zhu An Xu; Chun Mu Feng; Haijie Chen; Duck Young Chung; Vinayak P. Dravid; Guang Han Cao; Mercouri G. Kanatzidis

doi:10.1021/jacs.8b00465

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

Jin Ke Bao, Zhang Tu Tang, Hee Joon Jung, Ji Yong Liu, Yi Liu, Lin Li, Yu Ke Li, Zhu An Xu, Chun Mu Feng, Haijie Chen, Duck Young Chung, Vinayak P. Dravid, Guang Han Cao^*, Mercouri G. Kanatzidis

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

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 μ_B/Mn for H ∥ b and 1.37 μ_B/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 ΔS_mag ≈ 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.

Original language	English (US)
Pages (from-to)	4391-4400
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	140
Issue number	12
DOIs	https://doi.org/10.1021/jacs.8b00465
State	Published - Mar 28 2018

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.8b00465

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@article{12846e3786a04128827175cf48f622f9,

title = "Unique [Mn6Bi5]- Nanowires in KMn6Bi5: A Quasi-One-Dimensional Antiferromagnetic Metal",

abstract = "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) {\AA}, b = 4.6128(3) {\AA}, c = 13.3830(13) {\AA} 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 ΔSmag ≈ 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.",

author = "Bao, {Jin Ke} and Tang, {Zhang Tu} and Jung, {Hee Joon} and Liu, {Ji Yong} and Yi Liu and Lin Li and Li, {Yu Ke} and Xu, {Zhu An} and Feng, {Chun Mu} and Haijie Chen and Chung, {Duck Young} and Dravid, {Vinayak P.} and Cao, {Guang Han} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: Work at Argonne National Laboratory primarily was supported by the U.S. Department of Energy, Office of Science, Materials Sciences and Engineering. The SEM work was done by use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. The TEM work made use of the EPIC facility of Northwestern University's NU Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Physical property measurements performed in China were supported by the National Natural Science Foundation of China (grant no. 11674281) and National Key Research and Development Program of China (no. 2017YFA0303002). The authors thank Prof. M. Y. Yuan for his assist in EDS measurements, Dr. F. Han at ANL for his advice in single crystal diffraction, and Dr. Q. Tao and H. Bai for their help with magnetic property measurements. The authors thank Dr. D. Phelan at ANL for his helpful discussions. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = mar,

day = "28",

doi = "10.1021/jacs.8b00465",

language = "English (US)",

volume = "140",

pages = "4391--4400",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Unique [Mn6Bi5]- Nanowires in KMn6Bi5

T2 - A Quasi-One-Dimensional Antiferromagnetic Metal

AU - Bao, Jin Ke

AU - Tang, Zhang Tu

AU - Jung, Hee Joon

AU - Liu, Ji Yong

AU - Liu, Yi

AU - Li, Lin

AU - Li, Yu Ke

AU - Xu, Zhu An

AU - Feng, Chun Mu

AU - Chen, Haijie

AU - Chung, Duck Young

AU - Dravid, Vinayak P.

AU - Cao, Guang Han

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: Work at Argonne National Laboratory primarily was supported by the U.S. Department of Energy, Office of Science, Materials Sciences and Engineering. The SEM work was done by use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. The TEM work made use of the EPIC facility of Northwestern University's NU Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Physical property measurements performed in China were supported by the National Natural Science Foundation of China (grant no. 11674281) and National Key Research and Development Program of China (no. 2017YFA0303002). The authors thank Prof. M. Y. Yuan for his assist in EDS measurements, Dr. F. Han at ANL for his advice in single crystal diffraction, and Dr. Q. Tao and H. Bai for their help with magnetic property measurements. The authors thank Dr. D. Phelan at ANL for his helpful discussions. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/3/28

Y1 - 2018/3/28

N2 - 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 ΔSmag ≈ 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.

AB - 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 ΔSmag ≈ 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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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

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

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CSD 1870058: Experimental Crystal Structure Determination

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

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CSD 1870058: Experimental Crystal Structure Determination

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