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Title: Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

Abstract

To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP 2S 6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP 2S 7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie–Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP 2S 7 sample. UV–vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1527338
Grant/Contract Number:  
SC0018739; SC0016575
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 9; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Klepov, Vladislav V., Breton, Logan S., Pace, Kristen A., Kocevski, Vancho, Besmann, Theodore M., and zur Loye, Hans-Conrad. Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b00806.
Klepov, Vladislav V., Breton, Logan S., Pace, Kristen A., Kocevski, Vancho, Besmann, Theodore M., & zur Loye, Hans-Conrad. Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux. United States. doi:10.1021/acs.inorgchem.9b00806.
Klepov, Vladislav V., Breton, Logan S., Pace, Kristen A., Kocevski, Vancho, Besmann, Theodore M., and zur Loye, Hans-Conrad. Tue . "Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux". United States. doi:10.1021/acs.inorgchem.9b00806.
@article{osti_1527338,
title = {Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux},
author = {Klepov, Vladislav V. and Breton, Logan S. and Pace, Kristen A. and Kocevski, Vancho and Besmann, Theodore M. and zur Loye, Hans-Conrad},
abstractNote = {To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP2S6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP2S7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie–Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP2S7 sample. UV–vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.},
doi = {10.1021/acs.inorgchem.9b00806},
journal = {Inorganic Chemistry},
number = 9,
volume = 58,
place = {United States},
year = {2019},
month = {4}
}

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This content will become publicly available on April 23, 2020
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