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

Here, the perovskite manganites AMnO 3 and their doped analogues A 1–x B x MnO 3 (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 [Ce 3Mn 8O 8(O 2CPh) 18(HO 2CPh) 2] (Ce III 2Ce IVMn III 8; hereafter Ce 3Mn 8) bears a striking structural resemblance to the repeating unit seen in the perovskite manganites. Further, magnetic studies have established that Ce 3Mn 8 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.
Authors:
 [1] ;  [2] ;  [2] ;  [1] ;  [2] ;  [2] ;  [1]
  1. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
  2. Univ. of Florida, Gainesville, FL (United States). Dept. of Physics
Publication Date:
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1489401

Thuijs, Annaliese E., Li, Xiang -Guo, Wang, Yun -Peng, Abboud, Khalil A., Zhang, X. -G., Cheng, Hai -Ping, and Christou, George. Molecular analogue of the perovskite repeating unit and evidence for direct MnIII-CeIV-MnIII exchange coupling pathway. United States: N. p., Web. doi:10.1038/s41467-017-00642-0.
Thuijs, Annaliese E., Li, Xiang -Guo, Wang, Yun -Peng, Abboud, Khalil A., Zhang, X. -G., Cheng, Hai -Ping, & Christou, George. Molecular analogue of the perovskite repeating unit and evidence for direct MnIII-CeIV-MnIII exchange coupling pathway. United States. doi:10.1038/s41467-017-00642-0.
Thuijs, Annaliese E., Li, Xiang -Guo, Wang, Yun -Peng, Abboud, Khalil A., Zhang, X. -G., Cheng, Hai -Ping, and Christou, George. 2017. "Molecular analogue of the perovskite repeating unit and evidence for direct MnIII-CeIV-MnIII exchange coupling pathway". United States. doi:10.1038/s41467-017-00642-0. https://www.osti.gov/servlets/purl/1489401.
@article{osti_1489401,
title = {Molecular analogue of the perovskite repeating unit and evidence for direct MnIII-CeIV-MnIII exchange coupling pathway},
author = {Thuijs, Annaliese E. and Li, Xiang -Guo and Wang, Yun -Peng and Abboud, Khalil A. and Zhang, X. -G. and Cheng, Hai -Ping and Christou, George},
abstractNote = {Here, the perovskite manganites AMnO3 and their doped analogues A1–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] (CeIII 2CeIVMnIII 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 MnIII 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 MnIII 2 exchange couplings via superexchange pathways through bridging ligands but also an unusual, direct MnIII–CeIV–MnIII metal-to-metal channel involving the CeIV f orbitals.},
doi = {10.1038/s41467-017-00642-0},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {9}
}

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