Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates. / Nehrkorn, Joscha; Veber, Sergey L.; Zhukas, Liudmila A. и др.
в: Inorganic Chemistry, Том 57, № 24, 17.12.2018, стр. 15330-15340.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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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