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Advanced spectroscopic studies of (PPh4)2[Co(N3)4], a field-induced single-ion magnet.

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Title: Advanced spectroscopic studies of (PPh4)2[Co(N3)4], a field-induced single-ion magnet.
Authors: Hand, Adam T., Fakolujo, Adiat A., Krzystek, J., Ozerov, Mykhaylo, Daemen, Luke L., Xing, Jie, Gai, Zheng, Jin, Rongying, Telser, Joshua, Podlesnyak, Andrey A., Xue, Zi-Ling
Source: New Journal of Chemistry; 10/21/2025, Vol. 49 Issue 39, p17084-17098, 15p
Subject Terms: MAGNETIC anisotropy, MAGNETIC properties, ANISOTROPY, MAGNETS, SPECTROMETRY, LIGAND field theory, COBALT compounds, MAGNETOMETERS
Abstract: The high-spin CoII complex (PPh4)2[Co(N3)4] (Co-N3) has been investigated using advanced spectroscopic techniques [far-IR magneto-spectroscopy (FIRMS), high-frequency and high-field EPR (HFEPR), and inelastic neutron scattering (INS)] to study its zero-field-splitting (ZFS), giving spin-Hamiltonian (SH) parameters. The analysis of multi-frequency HFEPR reveals the easy-axis anisotropy with a D value of −10.39(5) cm−1 and a rhombic ratio (E/D) of 0.21(1). The magnetic properties have also been probed by direct-current (DC) magnetometry, suggesting minor differences in anisotropy from the previously reported polymorph (Co-N3′). Ligand-field theory (LFT) analysis indicates that the structures of Co-N3 and Co-N3′ are closer to D2d symmetry than other symmetries considered. Alternate-current (AC) susceptibility reveals slow magnetic relaxation under an applied field, indicating that Co-N3 is a field-induced single-ion magnet (SIM). While both Co-N3 and Co-N3′ were studied by DC magnetometry, one unusual aspect of the current work on Co-N3 is that advanced spectroscopies HFEPR, FIRMS, and INS were used to directly observe transitions between ZFS split states, giving accurate SH parameters. [ABSTRACT FROM AUTHOR]
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Description
Abstract:The high-spin Co<sup>II</sup> complex (PPh<subscript>4</subscript>)<subscript>2</subscript>[Co(N<subscript>3</subscript>)<subscript>4</subscript>] (Co-N<subscript>3</subscript>) has been investigated using advanced spectroscopic techniques [far-IR magneto-spectroscopy (FIRMS), high-frequency and high-field EPR (HFEPR), and inelastic neutron scattering (INS)] to study its zero-field-splitting (ZFS), giving spin-Hamiltonian (SH) parameters. The analysis of multi-frequency HFEPR reveals the easy-axis anisotropy with a D value of −10.39(5) cm<sup>−1</sup> and a rhombic ratio (E/D) of 0.21(1). The magnetic properties have also been probed by direct-current (DC) magnetometry, suggesting minor differences in anisotropy from the previously reported polymorph (Co-N<subscript>3</subscript>′). Ligand-field theory (LFT) analysis indicates that the structures of Co-N<subscript>3</subscript> and Co-N<subscript>3</subscript>′ are closer to D<subscript>2d</subscript> symmetry than other symmetries considered. Alternate-current (AC) susceptibility reveals slow magnetic relaxation under an applied field, indicating that Co-N<subscript>3</subscript> is a field-induced single-ion magnet (SIM). While both Co-N<subscript>3</subscript> and Co-N<subscript>3</subscript>′ were studied by DC magnetometry, one unusual aspect of the current work on Co-N<subscript>3</subscript> is that advanced spectroscopies HFEPR, FIRMS, and INS were used to directly observe transitions between ZFS split states, giving accurate SH parameters. [ABSTRACT FROM AUTHOR]
ISSN:11440546
DOI:10.1039/d5nj01857a