Lanthanide Borocarbides Ln3BC2Xn (Ln = La-Pr; X = H, F, Cl) Grown from Metal Flux: From Magnetic Ordering to Superconductivity

James T. Larson; Katelyn Wix; Olatunde Oladehin; Ryan Baumbach; Xiaoping Wang; Susan E. Latturner

doi:10.1021/acs.chemmater.4c02111

Lanthanide Borocarbides Ln₃BC₂X_n (Ln = La-Pr; X = H, F, Cl) Grown from Metal Flux: From Magnetic Ordering to Superconductivity

James T. Larson
, Katelyn Wix
, Olatunde Oladehin
, Ryan Baumbach
, Xiaoping Wang
, Susan E. Latturner

Single Crystal Diffraction

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

1 Scopus citations

Abstract

New stuffed lanthanide borocarbides were grown from reactions in lanthanide-rich eutectic melts, exploring the use of C₁₄H₁₀ (anthracene), C₁₂F₁₀ (decafluorobiphenyl), and LnCl₃ as sources of interstitial hydride, fluoride, and chloride ions. Ln₃BC₂X_n (Ln = La, Ce, Pr; X = H, F) are analogues of the orthorhombic Ca₃C₃Cl₂ structure type, featuring borocarbide units in place of the allenylide anions and small anions (X = H and F) in place of the chloride anions, partially occupying octahedral and tetrahedral interstitial sites surrounded by lanthanide cations. Single-crystal neutron diffraction data for La₃BC₂H_1.69 confirm that hydrogen is present in both interstitial sites, with site-splitting in the octahedral site. Magnetic studies and resistivity measurements indicate that La₃BC₂H_1.69 shows superconductivity with a T_c near 4.5 K. Pr₃BC₂H_x shows ferromagnetic ordering below 55 K, while the fluoride analogue Pr₃BC₂F_0.71 is paramagnetic. Attempts to incorporate chlorine into the interstitial sites lead to a structure change to the La₃BC₂Br₂ structure type.

Original language	English
Pages (from-to)	600-609
Number of pages	10
Journal	Chemistry of Materials
Volume	37
Issue number	2
DOIs	https://doi.org/10.1021/acs.chemmater.4c02111
State	Published - Jan 28 2025

Funding

This project was supported by the National Science Foundation Division of Materials Research (DMR-2126077). This work used the X-ray Characterization Center in the FSU Department of Chemistry and Biochemistry (FSU075000XRAY), as well as the Scanning Electron Microscope in the Biological Sciences Imaging Resource (BSIR) of the FSU Department of Biology. Single-crystal neutron diffraction data were collected using the TOPAZ instrument (BL-12) at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

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10.1021/acs.chemmater.4c02111

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title = "Lanthanide Borocarbides Ln3BC2Xn (Ln = La-Pr; X = H, F, Cl) Grown from Metal Flux: From Magnetic Ordering to Superconductivity",

abstract = "New stuffed lanthanide borocarbides were grown from reactions in lanthanide-rich eutectic melts, exploring the use of C14H10 (anthracene), C12F10 (decafluorobiphenyl), and LnCl3 as sources of interstitial hydride, fluoride, and chloride ions. Ln3BC2Xn (Ln = La, Ce, Pr; X = H, F) are analogues of the orthorhombic Ca3C3Cl2 structure type, featuring borocarbide units in place of the allenylide anions and small anions (X = H and F) in place of the chloride anions, partially occupying octahedral and tetrahedral interstitial sites surrounded by lanthanide cations. Single-crystal neutron diffraction data for La3BC2H1.69 confirm that hydrogen is present in both interstitial sites, with site-splitting in the octahedral site. Magnetic studies and resistivity measurements indicate that La3BC2H1.69 shows superconductivity with a Tc near 4.5 K. Pr3BC2Hx shows ferromagnetic ordering below 55 K, while the fluoride analogue Pr3BC2F0.71 is paramagnetic. Attempts to incorporate chlorine into the interstitial sites lead to a structure change to the La3BC2Br2 structure type.",

author = "Larson, \{James T.\} and Katelyn Wix and Olatunde Oladehin and Ryan Baumbach and Xiaoping Wang and Latturner, \{Susan E.\}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2025",

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doi = "10.1021/acs.chemmater.4c02111",

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T1 - Lanthanide Borocarbides Ln3BC2Xn (Ln = La-Pr; X = H, F, Cl) Grown from Metal Flux

T2 - From Magnetic Ordering to Superconductivity

AU - Larson, James T.

AU - Wix, Katelyn

AU - Oladehin, Olatunde

AU - Baumbach, Ryan

AU - Wang, Xiaoping

AU - Latturner, Susan E.

PY - 2025/1/28

Y1 - 2025/1/28

N2 - New stuffed lanthanide borocarbides were grown from reactions in lanthanide-rich eutectic melts, exploring the use of C14H10 (anthracene), C12F10 (decafluorobiphenyl), and LnCl3 as sources of interstitial hydride, fluoride, and chloride ions. Ln3BC2Xn (Ln = La, Ce, Pr; X = H, F) are analogues of the orthorhombic Ca3C3Cl2 structure type, featuring borocarbide units in place of the allenylide anions and small anions (X = H and F) in place of the chloride anions, partially occupying octahedral and tetrahedral interstitial sites surrounded by lanthanide cations. Single-crystal neutron diffraction data for La3BC2H1.69 confirm that hydrogen is present in both interstitial sites, with site-splitting in the octahedral site. Magnetic studies and resistivity measurements indicate that La3BC2H1.69 shows superconductivity with a Tc near 4.5 K. Pr3BC2Hx shows ferromagnetic ordering below 55 K, while the fluoride analogue Pr3BC2F0.71 is paramagnetic. Attempts to incorporate chlorine into the interstitial sites lead to a structure change to the La3BC2Br2 structure type.

AB - New stuffed lanthanide borocarbides were grown from reactions in lanthanide-rich eutectic melts, exploring the use of C14H10 (anthracene), C12F10 (decafluorobiphenyl), and LnCl3 as sources of interstitial hydride, fluoride, and chloride ions. Ln3BC2Xn (Ln = La, Ce, Pr; X = H, F) are analogues of the orthorhombic Ca3C3Cl2 structure type, featuring borocarbide units in place of the allenylide anions and small anions (X = H and F) in place of the chloride anions, partially occupying octahedral and tetrahedral interstitial sites surrounded by lanthanide cations. Single-crystal neutron diffraction data for La3BC2H1.69 confirm that hydrogen is present in both interstitial sites, with site-splitting in the octahedral site. Magnetic studies and resistivity measurements indicate that La3BC2H1.69 shows superconductivity with a Tc near 4.5 K. Pr3BC2Hx shows ferromagnetic ordering below 55 K, while the fluoride analogue Pr3BC2F0.71 is paramagnetic. Attempts to incorporate chlorine into the interstitial sites lead to a structure change to the La3BC2Br2 structure type.

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Lanthanide Borocarbides Ln₃BC₂X_n (Ln = La-Pr; X = H, F, Cl) Grown from Metal Flux: From Magnetic Ordering to Superconductivity

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