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Title: Structure, properties, and disorder in the new distorted-Hollandite PbIr 4 Se 8

Authors:
;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1396792
Grant/Contract Number:
AC02–06CH11357
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 242; Journal Issue: P1; Related Information: CHORUS Timestamp: 2017-10-04 15:36:15; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English

Citation Formats

Trump, Benjamin A., and McQueen, Tyrel M. Structure, properties, and disorder in the new distorted-Hollandite PbIr 4 Se 8. United States: N. p., 2016. Web. doi:10.1016/j.jssc.2016.07.005.
Trump, Benjamin A., & McQueen, Tyrel M. Structure, properties, and disorder in the new distorted-Hollandite PbIr 4 Se 8. United States. doi:10.1016/j.jssc.2016.07.005.
Trump, Benjamin A., and McQueen, Tyrel M. 2016. "Structure, properties, and disorder in the new distorted-Hollandite PbIr 4 Se 8". United States. doi:10.1016/j.jssc.2016.07.005.
@article{osti_1396792,
title = {Structure, properties, and disorder in the new distorted-Hollandite PbIr 4 Se 8},
author = {Trump, Benjamin A. and McQueen, Tyrel M.},
abstractNote = {},
doi = {10.1016/j.jssc.2016.07.005},
journal = {Journal of Solid State Chemistry},
number = P1,
volume = 242,
place = {United States},
year = 2016,
month =
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jssc.2016.07.005

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  • The synthesis and physical properties of the new distorted-Hollandite PbIr{sub 4}Se{sub 8} are reported. Powder X-ray diffraction and transmission electron microscopy show that the structure consists of edge- and corner-sharing IrSe{sub 6} octahedra, with one-dimensional channels occupied by Pb. The structure contains Se-Se anion-anion bonding, leading to an electron count of Pb{sup 2+}(Ir{sup 3+}){sub 4}(Se{sub 2}){sup 2-}(Se{sup 2−}){sub 6}, confirmed by bond-valence sums and diamagnetic behavior. Structural and heat capacity measurements demonstrate disorder on the Pb site, due to the combination of lone-pair effects and the large size of the one-dimensional channels. Comparisons are made to known Hollandite and pseudo-Hollanditemore » structures, which demonstrates that the anion-anion bonding in PbIr{sub 4}Se{sub 8} distorts its structure, to accommodate the Ir{sup 3+} state. An electronic structure calculation indicates semiconductor character with a band gap of 0.76(11) eV.« less
  • We report the synthesis and structural characterization of the new Ir holladite, Rb{sub 0.17}IrO{sub 2}. Rb{sub 0.17}IrO{sub 2} crystallizes in the tetragonal hollandite structure. In contrast to the previously reported monoclinic Ir hollandite K{sub 0.25}IrO{sub 2}, we do not observe a difference in Ir–O bond lengths in Rb{sub 0.17}IrO{sub 2} and thus find Ir in an average oxidation state of + 3.83. We also report and compare the electronic and magnetic properties of Rb{sub 0.17}IrO{sub 2} and K{sub 0.25}IrO{sub 2}, finding that they are both metallic and Pauli paramagnets further supporting that the electrons are delocalized in the Ir 5dmore » states. - Graphical abstract: Crystal structure of Rb{sub 0.17}IrO{sub 2} (right), and the SEM image of Rb{sub 0.17}IrO{sub 2}, showing the growth of thin needles (left). Display Omitted - Highlights: • New iridium hollandite. • Naturally grows in very thin wires. • Elementary physical properties of Ir holladites reported for the first time metallic conductor and paramagnetic.« less