Spin relaxation and resonant phonon trapping in[Gd2(fum)3(H<

Slow Magnetic Relaxation in a Palladium–Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion

“…This is a clear confirmation of the induced magnetic anisotropy along the bc ‐45° direction, which is consistent with a large contribution from the Pd−Gd bond to the observed magnetic relaxation. The observed splitting is similar to that for Gd 3+ systems with S= 7/2 previously reported . This might be due to a spin state of the Gd 3+ ion other than 7/2, which implies possible charge transfer to form Gd 2+ and Pd 3+ ions.…”

“…This is attributed to the perpendicular alignment of the crystal structure as seen in the crystal packing (Figure S3 in the Supporting Information), leading to contributions from the axis other than the Pd−Gd bond axis (Figures and S11 in the Supporting Information). The values of (Δ B ), | D |, and | E | are significantly larger than those for previously reported Gd‐based molecular magnets exhibiting slow magnetic relaxation ,. The values indicate that there is coupling between the ground and the excited states of the Gd ion, which causes Zeeman splitting, leading to the observed magnetic anisotropy in the Pd−Gd bond.…”

“…The bc‐ 45° axis coincides with the Pd−Gd bond axis (inset of Figure S11 in the Supporting Information), which makes it the easy axis of magnetization. The asymmetric absorption in the EPR spectra is a clear indication of axial distortion along the Pd−Gd bond axis. This is a clear confirmation of the induced magnetic anisotropy along the bc ‐45° direction, which is consistent with a large contribution from the Pd−Gd bond to the observed magnetic relaxation.…”

“…Therefore, the Gd ion in 1 was concluded to be in the +3 state as it is difficult to quantify the partial charge transferred to the Gd ion at this point. Second, we believe that the electron density donation from the 4d orbital of Pd 2+ to the hybridized 6p z , 5d xz , or 5d yz of Gd 3+ is sufficient to cause axial perturbation along the bc ‐45° axis, which corresponds to the Pd−Gd bond axis, leading to the observed EPR split . The Pd K‐edge XANES spectra for complexes 1 and 4 were obtained and compared with those for Pd 3 AcO 6 and Pd foil (Figures and S15 in the Supporting Information).…”

Slow magnetic relaxation in Ni–Ln (Ln = Ce, Gd, Dy) dinuclear complexes

“…Despite its essentially isotropic ground state with L = 0, several materials have been reported for which magnetic anisotropy around the gadolinium(III) centre was induced by local coordination, magnetic exchange coupling or electron density donation. [20][21][22][23][24][25][26][27][28][29] These materials containing gadolinium(III) may be considered as members of a new class of SMMs with the highest known spin state (4f 7 ) for a single ion.…”