Periodicity of Single‐Molecule Magnet Behaviour of Heterotetranuclear Lanthanide Complexes across the Lanthanide Series: A Compendium

Abstract

Acetato‐bridged palladium–lanthanide tetranuclear heterometallic complexes of the form [Pd2Ln2(H2O)2(CH3COO)10]⋅2 CH3COOH [Ln2=Ce2 (1), Pr2 (2), Nd2 (3), Sm2 (4), Tb2 (5), Dy2 (6), Dy0.2Y1.8 (6′′), Ho2 (7), Er2 (8), Er0.24Y1.7 (8′′), Tm2 (9), Yb2 (10), Y2(11)] were synthesised and characterised by experimental and theoretical techniques. All complexes containing Kramers lanthanide ions [Ln3+=Ce (1), Nd (3), Sm (4), Dy (6), DyY (6′′), Er (8), ErY (8′′), Yb (10)] showed field‐induced slow magnetic relaxation, characteristic of single‐molecule magnetism and purely of molecular origin. In contrast, all non‐Kramers lanthanide ions [Ln3+=Pr (2), Tb (5), Ho (7), Tm (9), Y3+ (11) is diamagnetic and non‐lanthanide] did not show any slow magnetic relaxation. The variation in the electronic structure and accompanying consequences across the complexes representing all Kramers and non‐Kramers lanthanide ions were investigated. The origin of the magnetic properties and the extent to which the axial donor–acceptor interaction involving the lanthanide ions and an electron‐deficient orbital of palladium affects the observed magnetic and electronic properties across the lanthanide series are presented. Unique consistent electronic and magnetic properties of isostructural complexes spanning the lanthanide series with properties dependent on whether the ions are Kramers or non‐Kramers are reported.

Magnetic Anisotropy Trends along a Full 4f-Series: The fn+7 Effect

“…Deep comprehension of the factors determining magnetic anisotropy is the key for improving the performances of lanthanide-based magnetic materials, already used in a wide range of different fields ranging from biochemistry to medicine, from solid state physics to cryogenics. , Synthetic chemists are nowadays able to tailor ligands with a suitable number and position of donor atoms to enhance the magnetic anisotropy of the magnetic ion and avoid interactions that can lead to unfavorable effects on magnetic properties. − The quest to find periodic correlations and establish whether a theoretical model is robust enough to predict properties of the entire lanthanide series makes the collection of data on several isostructural Ln complexes highly desirable. While magnetic studies on the second half of the series (Tb to Yb) are common, publications dealing with both heavy and light lanthanides are extremely rich in information but rare. − Even if this might seem astonishing, to the best of our knowledge there are no studies on magnetic properties of complete series (all 13 magnetic elements, from Ce to Yb) of mononuclear Ln molecular compounds.…”

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

“…Heterometallic complexes have been studied in many research fields such as luminescence, [1][2][3] catalysis, [4][5][6] and magnetism. [7][8][9][10][11][12][13][14] Luminescence has received particular interest because of its utilization in luminescence devices, bioimaging systems, and photosensitizers. Hasegawa et al…”

“…Considerable efforts have thus been devoted to the formation of various intermetallic interactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] Although highresolution X-ray diffraction analysis can provide insight into the electron density of bonds, 19 theoretical calculations are widely conducted for examining intermetallic interactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] In this study, we synthesized heterometallic Ln-Pt complexes:…”

Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

“…Heterometallic complexes have been studied in many research fields such as luminescence, − catalysis, − and magnetism. − Luminescence has received particular interest because of its utilization in luminescence devices, bioimaging systems, and photosensitizers. Hasegawa et al reported the thermocontrol emission of a heterometallic Tb­(III)–Eu­(III) polymer, wherein the energy transfer from the Tb to Eu ion is governed by the thermosensitivity dependence on linker ligands.…”

“…Thus, heterometallic interactions also exert an important influence on the physical properties of heterometallic complexes. Considerable efforts have thus been devoted to the formation of various intermetallic interactions. − Although high-resolution X-ray diffraction analysis can provide insight into the electron density of bonds, theoretical calculations are widely conducted for examining intermetallic interactions. − …”