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Title: Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy

Abstract

We synthesized and studied three mononuclear cobalt(II) tetranitrate complexes (A) 2[Co(NO 3) 4] with different countercations, Ph 4P + (1), MePh 3P + (2), and Ph 4As + (3), using X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. Furthermore, the X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 1–3 corresponds to the zero-field splitting (2(D 2 + 3E 2) 1/2) from 22.5(2) cm –1 in 1 to 26.6(3) cm –1 in 2 and 11.1(5) cm –1 in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm –1 for 1–3, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which ismore » a characteristic of field-induced single-molecule magnets (SMMs). Finally, the electronic structures and the origin of magnetic anisotropy of 1–3 were revealed by calculations at the CASPT2/NEVPT2 level.« less

Authors:
 [1];  [1];  [2];  [2];  [3];  [1];  [4];  [4];  [1];  [5];  [4];  [2]
  1. Nanjing Univ. (China). Collaborative Innovation Center of Advanced Microstructures and School of Chemistry and Chemical Engineering
  2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  3. Nanjing Normal Univ. (People's Republic of China). School of Physical Science and Technology
  4. Huazhong Univ. of Science and Technology, Wuhan (People's Republic of China). Wuhan National High Magnetic Field Center
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1341566
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Lei, Cui, Hui-Hui, Stavretis, Shelby E., Hunter, Seth C., Zhang, Yi-Quan, Chen, Xue-Tai, Sun, Yi-Chen, Wang, Zhenxing, Song, You, Podlesnyak, Andrey A., Ouyang, Zhong-Wen, and Xue, Zi-Ling. Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b01544.
Chen, Lei, Cui, Hui-Hui, Stavretis, Shelby E., Hunter, Seth C., Zhang, Yi-Quan, Chen, Xue-Tai, Sun, Yi-Chen, Wang, Zhenxing, Song, You, Podlesnyak, Andrey A., Ouyang, Zhong-Wen, & Xue, Zi-Ling. Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy. United States. doi:10.1021/acs.inorgchem.6b01544.
Chen, Lei, Cui, Hui-Hui, Stavretis, Shelby E., Hunter, Seth C., Zhang, Yi-Quan, Chen, Xue-Tai, Sun, Yi-Chen, Wang, Zhenxing, Song, You, Podlesnyak, Andrey A., Ouyang, Zhong-Wen, and Xue, Zi-Ling. Wed . "Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy". United States. doi:10.1021/acs.inorgchem.6b01544. https://www.osti.gov/servlets/purl/1341566.
@article{osti_1341566,
title = {Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy},
author = {Chen, Lei and Cui, Hui-Hui and Stavretis, Shelby E. and Hunter, Seth C. and Zhang, Yi-Quan and Chen, Xue-Tai and Sun, Yi-Chen and Wang, Zhenxing and Song, You and Podlesnyak, Andrey A. and Ouyang, Zhong-Wen and Xue, Zi-Ling},
abstractNote = {We synthesized and studied three mononuclear cobalt(II) tetranitrate complexes (A)2[Co(NO3)4] with different countercations, Ph4P+ (1), MePh3P+ (2), and Ph4As+ (3), using X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. Furthermore, the X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 1–3 corresponds to the zero-field splitting (2(D2 + 3E2)1/2) from 22.5(2) cm–1 in 1 to 26.6(3) cm–1 in 2 and 11.1(5) cm–1 in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm–1 for 1–3, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which is a characteristic of field-induced single-molecule magnets (SMMs). Finally, the electronic structures and the origin of magnetic anisotropy of 1–3 were revealed by calculations at the CASPT2/NEVPT2 level.},
doi = {10.1021/acs.inorgchem.6b01544},
journal = {Inorganic Chemistry},
number = 24,
volume = 55,
place = {United States},
year = {2016},
month = {12}
}

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Works referencing / citing this record:

CCDC 1412396: Experimental Crystal Structure Determination: BAHDAS : bis(methyl(triphenyl)phosphonium) tetrakis(nitrato)-cobalt(ii)
dataset, July 2015


CCDC 1422339: Experimental Crystal Structure Determination: PASCON11 : bis(tetraphenylarsonium) tetrakis(nitrato)-cobalt(ii)
dataset, September 2015


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journal, January 2019

  • Vassilyeva, Olga Yu.; Buvaylo, Elena A.; Kokozay, Vladimir N.
  • Dalton Transactions, Vol. 48, Issue 30
  • DOI: 10.1039/c9dt01642b

High-coordinate Co II and Fe II compounds constructed from an asymmetric tetradentate ligand show slow magnetic relaxation behavior
journal, January 2018

  • Huang, Xing-Cai; Qi, Zi-Yi; Ji, Cheng-Long
  • Dalton Transactions, Vol. 47, Issue 27
  • DOI: 10.1039/c8dt01829d

Single-ion magnetic anisotropy in a vacant octahedral Co( ii ) complex
journal, January 2019

  • Mondal, Amit Kumar; Jover, Jesús; Ruiz, Eliseo
  • Dalton Transactions, Vol. 48, Issue 1
  • DOI: 10.1039/c8dt03862g

Field-induced slow magnetic relaxation in pseudooctahedral cobalt( ii ) complexes with positive axial and large rhombic anisotropy
journal, January 2019

  • Świtlicka, Anna; Palion-Gazda, Joanna; Machura, Barbara
  • Dalton Transactions, Vol. 48, Issue 4
  • DOI: 10.1039/c8dt03965h

Anionic guest-dependent slow magnetic relaxation in Co( ii ) tripodal iminopyridine complexes
journal, January 2019

  • Klug, Christina M.; Ozumerzifon, Tarik J.; Bhowmick, Indrani
  • Dalton Transactions, Vol. 48, Issue 25
  • DOI: 10.1039/c9dt00739c

Long magnetic relaxation time of tetracoordinate Co 2+ in imidazo[1,5- a ]pyridinium-based (C 13 H 12 N 3 ) 2 [CoCl 4 ] hybrid salt and [Co(C 13 H 12 N 3 )Cl 3 ] molecular complex
journal, January 2019

  • Vassilyeva, Olga Yu.; Buvaylo, Elena A.; Kokozay, Vladimir N.
  • Dalton Transactions, Vol. 48, Issue 30
  • DOI: 10.1039/c9dt01642b