Spin Chains with Highly Quantum Character through Strong Covalency in Ca3CrN3

Linus Kautzsch; Alexandru B. Georgescu; Lin Ding Yuan; Keith M. Taddei; Aiden Reilly; Ram Seshadri; James M. Rondinelli; Stephen D. Wilson

doi:10.1021/jacs.4c11629

Spin Chains with Highly Quantum Character through Strong Covalency in Ca₃CrN₃

Linus Kautzsch^*, Alexandru B. Georgescu^*, Lin Ding Yuan, Keith M. Taddei, Aiden Reilly, Ram Seshadri, James M. Rondinelli^*, Stephen D. Wilson^*

^*Corresponding author for this work

Materials Science and Engineering

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

Abstract

The insulating transition metal nitride Ca₃CrN₃ consists of sheets of triangular [CrN₃]^6- units with C_2v symmetry that are connected via quasi-1D zigzag chains. Due to strong covalency between Cr and N, Cr³⁺ ions are unusually low-spin, and S = 1/2. Magnetic susceptibility measurements reveal dominant quasi-1D spin correlations with very large nearest-neighbor antiferromagnetic exchange J = 340 K and yet no sign of magnetic order down to T = 0.1 K. Density functional theory calculations are used to model the local electronic structure and the magnetic interactions, supporting the low-spin assignment of Cr³⁺ that is driven by strong π donation from the nitride ligands. The surprising failure of interchain exchange to drive long-range magnetic order is accounted for by the complex connectivity of the spin chain pairs that further frustrates order. Our combined results establish Ca₃CrN₃ as a nearly ideal manifestation of a quantum spin chain whose dynamics remain unquenched down to extraordinarily low temperatures despite strong near-neighbor exchange coupling.

Original language	English (US)
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.4c11629
State	Accepted/In press - 2025

Funding

J.M.R. thanks K.R. Poeppelmeier for helpful conversations on the chemistry of metal nitrido complexes and nitridometallates. This work was supported by the Air Force Office of Scientific Research under award number FA9550-23-1-0042. The research reported here made use of the shared facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara: NSF DMR-2308708. The UC Santa Barbara MRSEC is a member of the Materials Research Facilities Network (www.mrfn.org). This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. This research was supported in part by Lilly Endowment, Inc., through its support for the Indiana University Pervasive Technology Institute, and by Indiana University startup funds.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.4c11629

Cite this

@article{0514d839967643dba9ce55bcfd93f3fd,

title = "Spin Chains with Highly Quantum Character through Strong Covalency in Ca3CrN3",

abstract = "The insulating transition metal nitride Ca3CrN3 consists of sheets of triangular [CrN3]6- units with C2v symmetry that are connected via quasi-1D zigzag chains. Due to strong covalency between Cr and N, Cr3+ ions are unusually low-spin, and S = 1/2. Magnetic susceptibility measurements reveal dominant quasi-1D spin correlations with very large nearest-neighbor antiferromagnetic exchange J = 340 K and yet no sign of magnetic order down to T = 0.1 K. Density functional theory calculations are used to model the local electronic structure and the magnetic interactions, supporting the low-spin assignment of Cr3+ that is driven by strong π donation from the nitride ligands. The surprising failure of interchain exchange to drive long-range magnetic order is accounted for by the complex connectivity of the spin chain pairs that further frustrates order. Our combined results establish Ca3CrN3 as a nearly ideal manifestation of a quantum spin chain whose dynamics remain unquenched down to extraordinarily low temperatures despite strong near-neighbor exchange coupling.",

author = "Linus Kautzsch and Georgescu, {Alexandru B.} and Yuan, {Lin Ding} and Taddei, {Keith M.} and Aiden Reilly and Ram Seshadri and Rondinelli, {James M.} and Wilson, {Stephen D.}",

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society.",

year = "2025",

doi = "10.1021/jacs.4c11629",

language = "English (US)",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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T1 - Spin Chains with Highly Quantum Character through Strong Covalency in Ca3CrN3

AU - Kautzsch, Linus

AU - Georgescu, Alexandru B.

AU - Yuan, Lin Ding

AU - Taddei, Keith M.

AU - Reilly, Aiden

AU - Seshadri, Ram

AU - Rondinelli, James M.

AU - Wilson, Stephen D.

PY - 2025

Y1 - 2025

N2 - The insulating transition metal nitride Ca3CrN3 consists of sheets of triangular [CrN3]6- units with C2v symmetry that are connected via quasi-1D zigzag chains. Due to strong covalency between Cr and N, Cr3+ ions are unusually low-spin, and S = 1/2. Magnetic susceptibility measurements reveal dominant quasi-1D spin correlations with very large nearest-neighbor antiferromagnetic exchange J = 340 K and yet no sign of magnetic order down to T = 0.1 K. Density functional theory calculations are used to model the local electronic structure and the magnetic interactions, supporting the low-spin assignment of Cr3+ that is driven by strong π donation from the nitride ligands. The surprising failure of interchain exchange to drive long-range magnetic order is accounted for by the complex connectivity of the spin chain pairs that further frustrates order. Our combined results establish Ca3CrN3 as a nearly ideal manifestation of a quantum spin chain whose dynamics remain unquenched down to extraordinarily low temperatures despite strong near-neighbor exchange coupling.

AB - The insulating transition metal nitride Ca3CrN3 consists of sheets of triangular [CrN3]6- units with C2v symmetry that are connected via quasi-1D zigzag chains. Due to strong covalency between Cr and N, Cr3+ ions are unusually low-spin, and S = 1/2. Magnetic susceptibility measurements reveal dominant quasi-1D spin correlations with very large nearest-neighbor antiferromagnetic exchange J = 340 K and yet no sign of magnetic order down to T = 0.1 K. Density functional theory calculations are used to model the local electronic structure and the magnetic interactions, supporting the low-spin assignment of Cr3+ that is driven by strong π donation from the nitride ligands. The surprising failure of interchain exchange to drive long-range magnetic order is accounted for by the complex connectivity of the spin chain pairs that further frustrates order. Our combined results establish Ca3CrN3 as a nearly ideal manifestation of a quantum spin chain whose dynamics remain unquenched down to extraordinarily low temperatures despite strong near-neighbor exchange coupling.

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