LiMo8O10: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Zachary T. Messegee; Philippe Gall; Hari Bhandari; Peter E. Siegfried; Chang Jong Kang; Benjamin Chen; Carl R. Conti; Banghao Chen; Mark Croft; Qiang Zhang; Syed N. Qadri; Joseph Prestigiacomo; Nirmal J. Ghimire; Patrick Gougeon; Xiaoyan Tan

doi:10.1021/acs.inorgchem.2c01917

LiMo₈O₁₀: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Zachary T. Messegee, Philippe Gall, Hari Bhandari, Peter E. Siegfried, Chang Jong Kang, Benjamin Chen, Carl R. Conti, Banghao Chen, Mark Croft, Qiang Zhang, Syed N. Qadri, Joseph Prestigiacomo, Nirmal J. Ghimire, Patrick Gougeon, Xiaoyan Tan

Powder Diffraction

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

Abstract

Polycrystalline LiMo₈O₁₀was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I4₁md) is confirmed based on the Rietveld refinement of powder neutron diffraction and ⁷Li/⁶Li solid-state NMR. The crystal structure features infinite chains of Mo₄O₅(i.e., Mo₂Mo_4/2O_6/2O_6/3) as a repeat unit containing edge-sharing Mo₆octahedra with strong Mo-Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L₃edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo₈O₁₀is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott's variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ_1.8/ρ₃₀₀= 435. LiMo₈O₁₀shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

Original language	English
Pages (from-to)	13924-13932
Number of pages	9
Journal	Inorganic Chemistry
Volume	61
Issue number	35
DOIs	https://doi.org/10.1021/acs.inorgchem.2c01917
State	Published - Sep 5 2022

Funding

Z.T.M. and X.T. were supported by start-up funding from George Mason University. C.-J.K. was supported by the NRF grant (NRF-2022R1C1C1008200). N.J.G. acknowledges the support from the National Science Foundation (NSF) CAREER award DMR- 2143903. Transport measurements were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The XANES was performed at NSLS-II beamline 7-ID-2 SST-2, under the expert guidance of Conan Weiland (NIST). The National Synchrotron Light Source II (NSLS-II) is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract no DE-SC0012704. This work used resources at the Spallation Neutron Source, DOE Office of Science Facilities operated by the Oak Ridge National Laboratory. We thank Dr. David Walker at Columbia University for preparing the dense pellet with the Walker-type high-pressure press.

Access to Document

10.1021/acs.inorgchem.2c01917

Cite this

Messegee, Z. T., Gall, P., Bhandari, H., Siegfried, P. E., Kang, C. J., Chen, B., Conti, C. R., Chen, B., Croft, M., Zhang, Q., Qadri, S. N., Prestigiacomo, J., Ghimire, N. J., Gougeon, P., & Tan, X. (2022). LiMo₈O₁₀: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra. Inorganic Chemistry, 61(35), 13924-13932. https://doi.org/10.1021/acs.inorgchem.2c01917

@article{1a733fbfbaf64561932c1d745e70622b,

title = "LiMo8O10: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra",

abstract = "Polycrystalline LiMo8O10was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I41md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7Li/6Li solid-state NMR. The crystal structure features infinite chains of Mo4O5(i.e., Mo2Mo4/2O6/2O6/3) as a repeat unit containing edge-sharing Mo6octahedra with strong Mo-Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L3edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo8O10is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott's variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ1.8/ρ300= 435. LiMo8O10shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.",

author = "Messegee, {Zachary T.} and Philippe Gall and Hari Bhandari and Siegfried, {Peter E.} and Kang, {Chang Jong} and Benjamin Chen and Conti, {Carl R.} and Banghao Chen and Mark Croft and Qiang Zhang and Qadri, {Syed N.} and Joseph Prestigiacomo and Ghimire, {Nirmal J.} and Patrick Gougeon and Xiaoyan Tan",

year = "2022",

month = sep,

day = "5",

doi = "10.1021/acs.inorgchem.2c01917",

language = "English",

volume = "61",

pages = "13924--13932",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "35",

}

TY - JOUR

T1 - LiMo8O10

T2 - Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

AU - Messegee, Zachary T.

AU - Gall, Philippe

AU - Bhandari, Hari

AU - Siegfried, Peter E.

AU - Kang, Chang Jong

AU - Chen, Benjamin

AU - Conti, Carl R.

AU - Chen, Banghao

AU - Croft, Mark

AU - Zhang, Qiang

AU - Qadri, Syed N.

AU - Prestigiacomo, Joseph

AU - Ghimire, Nirmal J.

AU - Gougeon, Patrick

AU - Tan, Xiaoyan

PY - 2022/9/5

Y1 - 2022/9/5

N2 - Polycrystalline LiMo8O10was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I41md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7Li/6Li solid-state NMR. The crystal structure features infinite chains of Mo4O5(i.e., Mo2Mo4/2O6/2O6/3) as a repeat unit containing edge-sharing Mo6octahedra with strong Mo-Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L3edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo8O10is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott's variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ1.8/ρ300= 435. LiMo8O10shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

AB - Polycrystalline LiMo8O10was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I41md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7Li/6Li solid-state NMR. The crystal structure features infinite chains of Mo4O5(i.e., Mo2Mo4/2O6/2O6/3) as a repeat unit containing edge-sharing Mo6octahedra with strong Mo-Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L3edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo8O10is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott's variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ1.8/ρ300= 435. LiMo8O10shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

UR - http://www.scopus.com/inward/record.url?scp=85137161546&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.2c01917

DO - 10.1021/acs.inorgchem.2c01917

M3 - Article

C2 - 35993886

AN - SCOPUS:85137161546

SN - 0020-1669

VL - 61

SP - 13924

EP - 13932

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 35

ER -

LiMo₈O₁₀: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this