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Observation of Robust Compressed CuO<sub>6</sub> Octahedra and Exotic Spin Structure in CaCuFe<sub>2</sub>O<sub>5</sub>

Maocai Pi, Junye Yang, Jie Zhang, Xubin Ye, Xiao Wang, Lunhua He, Zhiwei Hu, Chien‐Te Chen, Chang‐Yang Kuo, Zhao Pan, Yao Shen, Youwen Long

2025Journal of the American Chemical Society5 citationsDOI

Abstract

CuO 6 octahedra usually show elongated distortion, leading to active d x 2 −y 2 orbitals and planar exchange interactions, while compressed CuO 6 octahedra with active d 3 z 2 − r 2 orbitals and unidirectional exchange interactions are exceptionally rare. Here, we design and synthesize a new frustrated antiferromagnet CaCuFe 2 O 5 through a high-pressure and high-temperature approach, in which robust compressed CuO 6 octahedra are realized, separating the Fe 2 O 5 sheets that comprise zigzag spin ladders. Magnetic susceptibility and specific heat measurements exhibit a long-range antiferromagnetic order below the Néel temperature of 165 K, which is further confirmed by neutron diffraction. Detailed magnetic refinement reveals a C-type spin structure, with its spin arrangement and orientation distinct from that of the isostructural CaFe 3 O 5 . By constructing a Heisenberg model, we find that this is due to the exchange redistribution between the CuO 6 octahedra and Fe 2 O 5 sheets, during which some of the exchange interactions are selectively annihilated due to the specific orientation of the Cu d 3 z 2 − r 2 orbitals in the compressed CuO 6 octahedra. Our results provide a unique example of robust compressed CuO 6 octahedra and show that it can selectively annihilate some of the exchange interactions and completely modify the spin structure and magnetic frustration accordingly.

Topics & Concepts

ChemistryOctahedronSpin (aerodynamics)CrystallographyCondensed matter physicsCrystal structureThermodynamicsPhysicsAdvanced Condensed Matter PhysicsPhysics of Superconductivity and MagnetismMagnetic and transport properties of perovskites and related materials
Observation of Robust Compressed CuO<sub>6</sub> Octahedra and Exotic Spin Structure in CaCuFe<sub>2</sub>O<sub>5</sub> | Litcius