Molecular analogue of the perovskite repeating unit and evidence for direct MnIII-CeIV-MnIII exchange coupling pathway

Thuijs, Annaliese E.; Li, Xiang -Guo; Wang, Yun -Peng; Abboud, Khalil A.; Zhang, X. -G.; Cheng, Hai -Ping; Christou, George

doi:10.1038/s41467-017-00642-0

Title: Molecular analogue of the perovskite repeating unit and evidence for direct Mn^III-Ce^IV-Mn^III exchange coupling pathway

Journal Article · 10 September 2017 · Nature Communications

DOI: https://doi.org/10.1038/s41467-017-00642-0 · OSTI ID:1489401

Thuijs, Annaliese E. ^[1]; Li, Xiang -Guo ^[2]; Wang, Yun -Peng ^[2]; Abboud, Khalil A. ^[1]; Zhang, X. -G. ^[2]; Cheng, Hai -Ping ^[2]; Christou, George ^[1]

Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
Univ. of Florida, Gainesville, FL (United States). Dept. of Physics

Here, the perovskite manganites AMnO₃ and their doped analogues A_1–x B _x MnO₃ (A and B = main group and lanthanide metals) are a fascinating family of magnetic oxides exhibiting a rich variety of properties. They are thus under intense investigation along multiple fronts, one of which is how their structural and physical properties are modified at the nanoscale. Here we show that the molecular compound [Ce₃Mn₈O₈(O₂CPh)₁₈(HO₂CPh)₂] (Ce^III ₂Ce^IVMn^III ₈; hereafter Ce₃Mn₈) bears a striking structural resemblance to the repeating unit seen in the perovskite manganites. Further, magnetic studies have established that Ce₃Mn₈ exhibits both the combination of pairwise Mn^III ₂ ferromagnetic and antiferromagnetic exchange interactions, and the resultant spin vector alignments that are found within the 3-D C-type antiferromagnetic perovskites. First-principles theoretical calculations reveal not only the expected nearest-neighbor Mn^III ₂ exchange couplings via superexchange pathways through bridging ligands but also an unusual, direct Mn^III–Ce^IV–Mn^III metal-to-metal channel involving the Ce^IV f orbitals.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center

Sponsoring Organization:: USDOE

OSTI ID:: 1489401

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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