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Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates. / Nehrkorn, Joscha; Veber, Sergey L.; Zhukas, Liudmila A. et al.

In: Inorganic Chemistry, Vol. 57, No. 24, 17.12.2018, p. 15330-15340.

Research output: Contribution to journal › Article › peer-review

Harvard

Nehrkorn, J, Veber, SL, Zhukas, LA, Novikov, VV, Nelyubina, YV, Voloshin, YZ, Holldack, K, Stoll, S & Schnegg, A 2018, 'Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates', Inorganic Chemistry, vol. 57, no. 24, pp. 15330-15340. https://doi.org/10.1021/acs.inorgchem.8b02670

APA

Nehrkorn, J., Veber, S. L., Zhukas, L. A., Novikov, V. V., Nelyubina, Y. V., Voloshin, Y. Z., Holldack, K., Stoll, S., & Schnegg, A. (2018). Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates. Inorganic Chemistry, 57(24), 15330-15340. https://doi.org/10.1021/acs.inorgchem.8b02670

Vancouver

Nehrkorn J, Veber SL, Zhukas LA, Novikov VV, Nelyubina YV, Voloshin YZ et al. Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates. Inorganic Chemistry. 2018 Dec 17;57(24):15330-15340. doi: 10.1021/acs.inorgchem.8b02670

Author

Nehrkorn, Joscha ; Veber, Sergey L. ; Zhukas, Liudmila A. et al. / Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 24. pp. 15330-15340.

BibTeX

@article{17b142a0bba44c3c82f27f9291e4d53a,
title = "Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates",
abstract = "Zero-field splitting (ZFS) of three high-spin Co(I) (S = 1) clathrochelate complexes was determined by frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). The following axial and rhombic ZFS values (D and E, respectively) were determined: [N(n-Bu)4]CoI(GmCl2)3(BPh)2 (1, D/hc = +16.43(1) cm-1, E/hc = 0.0(1) cm-1), [P(Me2N)4]CoI(GmCl2)3(BPh)2 (2, D/hc = +16.67(4) cm-1, E/hc = 0.0(1) cm-1), and [P(C6H5)4]CoI(GmCl2)3(BPh)2 (3, D/hc = +16.72(2) cm-1, E/hc = 0.24(3) cm-1). Complementary susceptibility χT measurements and quantum chemistry calculations on 1 revealed hard-axis-type magnetic anisotropy and allowed for a correlation of ZFS and the electronic structure. Increased rhombicity of 3 as compared to 1 and 2 was assigned to symmetry changes of the ligand structure induced by the change of the counterion. 1 and 3 exhibited temperature-dependent ZFS values. Possible reasons for this phenomenon, such as structural changes and weak chain-like intermolecular antiferromagnetic interactions, are discussed.",
keywords = "SINGLE-ION MAGNET, STATE PERTURBATION-THEORY, MOLECULE MAGNETS, BASIS-SETS, TRANSITION, VALENCE, ANISOTROPY, COMPLEXES, SPECTROSCOPY, FREQUENCY",
author = "Joscha Nehrkorn and Veber, {Sergey L.} and Zhukas, {Liudmila A.} and Novikov, {Valentin V.} and Nelyubina, {Yulia V.} and Voloshin, {Yan Z.} and Karsten Holldack and Stefan Stoll and Alexander Schnegg",
note = "Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",
year = "2018",
month = dec,
day = "17",
doi = "10.1021/acs.inorgchem.8b02670",
language = "English",
volume = "57",
pages = "15330--15340",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

}

RIS

TY - JOUR

T1 - Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates

AU - Nehrkorn, Joscha

AU - Veber, Sergey L.

AU - Zhukas, Liudmila A.

AU - Novikov, Valentin V.

AU - Nelyubina, Yulia V.

AU - Voloshin, Yan Z.

AU - Holldack, Karsten

AU - Stoll, Stefan

AU - Schnegg, Alexander

N1 - Publisher Copyright: Copyright © 2018 American Chemical Society.

PY - 2018/12/17

Y1 - 2018/12/17

N2 - Zero-field splitting (ZFS) of three high-spin Co(I) (S = 1) clathrochelate complexes was determined by frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). The following axial and rhombic ZFS values (D and E, respectively) were determined: [N(n-Bu)4]CoI(GmCl2)3(BPh)2 (1, D/hc = +16.43(1) cm-1, E/hc = 0.0(1) cm-1), [P(Me2N)4]CoI(GmCl2)3(BPh)2 (2, D/hc = +16.67(4) cm-1, E/hc = 0.0(1) cm-1), and [P(C6H5)4]CoI(GmCl2)3(BPh)2 (3, D/hc = +16.72(2) cm-1, E/hc = 0.24(3) cm-1). Complementary susceptibility χT measurements and quantum chemistry calculations on 1 revealed hard-axis-type magnetic anisotropy and allowed for a correlation of ZFS and the electronic structure. Increased rhombicity of 3 as compared to 1 and 2 was assigned to symmetry changes of the ligand structure induced by the change of the counterion. 1 and 3 exhibited temperature-dependent ZFS values. Possible reasons for this phenomenon, such as structural changes and weak chain-like intermolecular antiferromagnetic interactions, are discussed.

AB - Zero-field splitting (ZFS) of three high-spin Co(I) (S = 1) clathrochelate complexes was determined by frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). The following axial and rhombic ZFS values (D and E, respectively) were determined: [N(n-Bu)4]CoI(GmCl2)3(BPh)2 (1, D/hc = +16.43(1) cm-1, E/hc = 0.0(1) cm-1), [P(Me2N)4]CoI(GmCl2)3(BPh)2 (2, D/hc = +16.67(4) cm-1, E/hc = 0.0(1) cm-1), and [P(C6H5)4]CoI(GmCl2)3(BPh)2 (3, D/hc = +16.72(2) cm-1, E/hc = 0.24(3) cm-1). Complementary susceptibility χT measurements and quantum chemistry calculations on 1 revealed hard-axis-type magnetic anisotropy and allowed for a correlation of ZFS and the electronic structure. Increased rhombicity of 3 as compared to 1 and 2 was assigned to symmetry changes of the ligand structure induced by the change of the counterion. 1 and 3 exhibited temperature-dependent ZFS values. Possible reasons for this phenomenon, such as structural changes and weak chain-like intermolecular antiferromagnetic interactions, are discussed.

KW - SINGLE-ION MAGNET

KW - STATE PERTURBATION-THEORY

KW - MOLECULE MAGNETS

KW - BASIS-SETS

KW - TRANSITION

KW - VALENCE

KW - ANISOTROPY

KW - COMPLEXES

KW - SPECTROSCOPY

KW - FREQUENCY

UR - http://www.scopus.com/inward/record.url?scp=85058504388&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b02670

DO - 10.1021/acs.inorgchem.8b02670

M3 - Article

C2 - 30495930

AN - SCOPUS:85058504388

VL - 57

SP - 15330

EP - 15340

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -

ID: 17878927