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Title: High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets

Abstract

A series of dysprosium(III) metallocenium salts, [Dy(Cp iPr4R) 2][B(C 6F 5) 4] (R = H (1), Me (2), Et (3), iPr (4)), was synthesized by reaction of DyI 3 with the corresponding known NaCp iPr4R (R = H, iPr) and novel NaCp iPr4R (R = Me, Et) salts at high temperature, followed by iodide abstraction with [H(SiEt 3) 2][B(C 6F 5) 4]. Variation of the substituents in this series results in substantial changes in molecular structure, with more sterically-encumbering cyclopentadienyl ligands promoting longer Dy–C distances and larger Cp–Dy–Cp angles. Dc and ac magnetic susceptibility data reveal that these structural changes have a considerable impact on the magnetic relaxation behavior and operating temperature of each compound. In particular, the magnetic relaxation barrier increases as the Dy–C distance decreases and the Cp–Dy–Cp angle increases. An overall 45 K increase in the magnetic blocking temperature is observed across the series, with compounds 2–4 exhibiting the highest 100 s blocking temperatures yet reported for a single-molecule magnet. Compound 2 possesses the highest operating temperature of the series with a 100 s blocking temperature of 62 K. Concomitant increases in the effective relaxation barrier and the maximum magnetic hysteresis temperature are observed, with 2 displayingmore » a barrier of 1468 cm -1 and open magnetic hysteresis as high as 72 K at a sweep rate of 3.1 mT s -1. Magneto-structural correlations are discussed with the goal of guiding the synthesis of future high operating temperature Dy III metallocenium single-molecule magnets.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [3];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Naval Air Warfare Center Weapons Division, China Lake, CA (United States). Research Dept. Chemistry Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Naval Air Warfare Center Weapons Division, China Lake, CA (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1479158
Alternate Identifier(s):
OSTI ID: 1493250
Grant/Contract Number:  
AC02-05CH11231; CHE-1800252
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 45; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Randall McClain, K., Gould, Colin A., Chakarawet, Khetpakorn, Teat, Simon J., Groshens, Thomas J., Long, Jeffrey R., and Harvey, Benjamin G. High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets. United States: N. p., 2018. Web. doi:10.1039/c8sc03907k.
Randall McClain, K., Gould, Colin A., Chakarawet, Khetpakorn, Teat, Simon J., Groshens, Thomas J., Long, Jeffrey R., & Harvey, Benjamin G. High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets. United States. doi:10.1039/c8sc03907k.
Randall McClain, K., Gould, Colin A., Chakarawet, Khetpakorn, Teat, Simon J., Groshens, Thomas J., Long, Jeffrey R., and Harvey, Benjamin G. Thu . "High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets". United States. doi:10.1039/c8sc03907k.
@article{osti_1479158,
title = {High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets},
author = {Randall McClain, K. and Gould, Colin A. and Chakarawet, Khetpakorn and Teat, Simon J. and Groshens, Thomas J. and Long, Jeffrey R. and Harvey, Benjamin G.},
abstractNote = {A series of dysprosium(III) metallocenium salts, [Dy(CpiPr4R)2][B(C6F5)4] (R = H (1), Me (2), Et (3), iPr (4)), was synthesized by reaction of DyI3 with the corresponding known NaCpiPr4R (R = H, iPr) and novel NaCpiPr4R (R = Me, Et) salts at high temperature, followed by iodide abstraction with [H(SiEt3)2][B(C6F5)4]. Variation of the substituents in this series results in substantial changes in molecular structure, with more sterically-encumbering cyclopentadienyl ligands promoting longer Dy–C distances and larger Cp–Dy–Cp angles. Dc and ac magnetic susceptibility data reveal that these structural changes have a considerable impact on the magnetic relaxation behavior and operating temperature of each compound. In particular, the magnetic relaxation barrier increases as the Dy–C distance decreases and the Cp–Dy–Cp angle increases. An overall 45 K increase in the magnetic blocking temperature is observed across the series, with compounds 2–4 exhibiting the highest 100 s blocking temperatures yet reported for a single-molecule magnet. Compound 2 possesses the highest operating temperature of the series with a 100 s blocking temperature of 62 K. Concomitant increases in the effective relaxation barrier and the maximum magnetic hysteresis temperature are observed, with 2 displaying a barrier of 1468 cm-1 and open magnetic hysteresis as high as 72 K at a sweep rate of 3.1 mT s-1. Magneto-structural correlations are discussed with the goal of guiding the synthesis of future high operating temperature DyIII metallocenium single-molecule magnets.},
doi = {10.1039/c8sc03907k},
journal = {Chemical Science},
number = 45,
volume = 9,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c8sc03907k

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Cited by: 24 works
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Works referencing / citing this record:

CCDC 1865386: Experimental Crystal Structure Determination: WIRGUC : bis(pentamethylcyclopentadienyl)-dysprosium(iii) tetrakis(pentafluorophenyl)borate
dataset, September 2018

  • McClain, K. Randall; Gould, Colin A.; Chakarawet, Khetpakorn
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc20m2rh

CCDC 1865387: Experimental Crystal Structure Determination: WIRHAJ : bis(1,2,3,4-tetra-isopropyl-cyclopentadienyl)-dysprosium(iii) tetrakis(pentafluorophenyl)borate
dataset, September 2018

  • McClain, K. Randall; Gould, Colin A.; Chakarawet, Khetpakorn
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc20m2sj

CCDC 1873921: Experimental Crystal Structure Determination: WIRJAL : bis(penta-isopropyl-cyclopentadienyl)-yttrium(iii) tetrakis(pentafluorophenyl)borate
dataset, October 2018

  • McClain, K. Randall; Gould, Colin A.; Chakarawet, Khetpakorn
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc20wz2z

CCDC 1873924: Experimental Crystal Structure Determination: WIRJOZ : bis(1,2,3,4-tetra-isopropyl-cyclopentadienyl)-yttrium(iii) tetrakis(pentafluorophenyl)borate
dataset, October 2018

  • McClain, K. Randall; Gould, Colin A.; Chakarawet, Khetpakorn
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc20wz52