Cobalt-Based Single-Ion Magnets on an Apatite Lattice: Toward Patterned Arrays for Magnetic Memories

Single-ion magnets (SIMs) that can maintain magnetization direction on an individual transition metal atom represent the smallest atomic-scale units for future magnetic data storage devices and molecular electronics. Here we present a robust extended inorganic solid hosting efficient SIM centers, as an alternative to molecular SIM crystals. We show that unique dioxocobaltate­(II) ions, confined in the channels of strontium hydroxyapatite, exhibit classical SIM features with a large energy barrier for magnetization reversal (<i>U</i>_eff) of 51–59 cm^–1. The samples have been tuned such that a magnetization hysteresis opens below 8 K and <i>U</i>_eff increases by a factor of 4 and can be further enhanced to the highest values among 3d metal complexes of 275 cm^–1 when Ba is substituted for Sr. The SIM properties are preserved without any tendency toward spin ordering up to a high Co concentration. At a maximal Co content, a hypothetical regular hexagonal grid of SIMs with a 1 nm interspacing on the (001) crystal facet would allow a maximal magnetic recording density of 10⁵ Gb/cm²

Cobalt-Based Single-Ion Magnets on an Apatite Lattice: Toward Patterned Arrays for Magnetic Memories

Single-ion magnets (SIMs) that can maintain magnetization direction on an individual transition metal atom represent the smallest atomic-scale units for future magnetic data storage devices and molecular electronics. Here we present a robust extended inorganic solid hosting efficient SIM centers, as an alternative to molecular SIM crystals. We show that unique dioxocobaltate­(II) ions, confined in the channels of strontium hydroxyapatite, exhibit classical SIM features with a large energy barrier for magnetization reversal (<i>U</i>_eff) of 51–59 cm^–1. The samples have been tuned such that a magnetization hysteresis opens below 8 K and <i>U</i>_eff increases by a factor of 4 and can be further enhanced to the highest values among 3d metal complexes of 275 cm^–1 when Ba is substituted for Sr. The SIM properties are preserved without any tendency toward spin ordering up to a high Co concentration. At a maximal Co content, a hypothetical regular hexagonal grid of SIMs with a 1 nm interspacing on the (001) crystal facet would allow a maximal magnetic recording density of 10⁵ Gb/cm²

Slow Spin Relaxation in Dioxocobaltate(II) Anions Embedded in the Lattice of Calcium Hydroxyapatite

Pure-phase cobalt-doped calcium hydroxyapatite ceramic samples with composition Ca₁₀(PO₄)₆[(CoO₂)_<i>x</i>(OH)_{1–2<i>x</i>}]₂, where <i>x</i> = 0–0.2, were synthesized by high-temperature solid-state reaction, and their crystal structures, vibrational spectra, and magnetic properties were studied. Co atoms are found to enter into the apatite trigonal channel formally substituting H atoms and forming bent dioxocobaltate­(II) anions. The anion exhibits single-molecule-magnet (SMM) behavior: slow relaxation of magnetization below 8 K under a nonzero magnetic field with an energy barrier of 63 cm^–1. The barrier value does not depend on the concentration of Co ions, virtually coincides with the zero-field-splitting energy as determined from direct-current magnetization, and is very close to the value obtained earlier for cobalt-doped strontium hydroxyapatite. Moreover, the vibration frequencies of the dioxocobaltate­(II) anion are found to be the same in calcium and strontium apatite matrixes. The very weak dependence of the SMM parameters on the matrix nature in combination with good chemical and thermal stabilities of the compounds provides wide opportunities to exploit the intrinsic properties of such a SMM-like anion