Incorporating palladium in the first coordination sphere of acetato-bridged lanthanoid complexes, [Pd Ln (H O) (AcO) ]⋅2 AcOH (Ln=Gd (1), Y (2), Gd Y (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d Pd ion to Gd ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X-ray absorption near-edge structure (XANES) analysis. Field-induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre-exponential factor (τ =0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal-lanthanoid (TM-Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.

Heterometallic Gd-Pt complexes ([Gd Pt (H O) (SAc) ] (SAc=thioacetate), [Y Gd Pt (H O) (SAc) ], and [Gd Pt (H O) (SAc) ]⋅7 H O have been synthesized. The crystal structures and DFT calculations indicated a Gd-Pt heretometallic bond. Single-crystal ESR spectra determined the direction of magnetic anisotropy as direction of the Gd-Pt bond. In other words, the Gd-Pt bond dictates the direction of magnetic anisotropy. The heterometallic Gd-Pt bond lowers the symmetry of the Gd ion, splitting the Kramers doublet in a dc field. Thus, we observed clear field-induced slow magnetic relaxation of [Y Gd Pt (H O) (SAc) ] up to 36 K. The relaxation process was determined to be a direct process.

The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF)2[Co(pdms)2] (TTF = tetrathiafulvalene and H2pdms = 1,2-bis(methanesulfonamido)benzene), was electrochemically synthesized and investigated structurally, physically and theoretically. The quite close oxidation potential between neutral TTF and the coordination precursor, (HNEt3)2[M(pdms)2] (M = Co, Zn) causes multiple charge transfers (CTs) between SIM donor [M(pdms)2] nand the TTF •+ acceptor as well as an intra-donor CT from the pdms ligand to Co ion upon electrocrystallization. Usually TTF works as a donor, whereas in our system, TTF works as both a donor and an accepter due to the close oxidation potentials. Furthermore, the [M(pdms)2] ndonor and TTF •+ acceptor are not segregated but strongly interact with each other, contrary to reported layered donor-acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with the CT, cause relatively 2 high electrical conductivity to very low temperature. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops were observed. (TTF)2[Co(pdms)2] (2-Co) is an excellent building block for preparing new conductive SIM.

Heterometallic Ln-Pt complexes, with the formula [Ln2Pt3(H2O)2(SAc)12] (Ln = Ho(1), Er(2); SAc = thioacetate), were synthesized. From natural bond orbital (NBO) and local orbital locator (LOL) analyses and X-ray absorption fine structure (XAFS) measurements, it was clear that the Ln-Pt interactions or electron polarization occurred. Butterfly-type hysteresis was observed for both 1 and 2. 1 and 2 underwent field-induced slow magnetic relaxation up to 4 K. These magnetic properties were induced by Ln-Pt electron polarization.

The X-ray crystal structure of the title phthalazin-1-one derivative, C17H16N2O3S {systematic name: 2-[(2,4,6-trimethylbenzene)sulfonyl]-1,2-dihydrophthalazin-1-one}, features a tetrahedral sulfoxide-S atom, connected to phthalazin-1-one and mesityl residues. The dihedral angle [83.26 (4)°] between the organic substituents is consistent with the molecule having the shape of the letter V. In the crystal, phthalazinone-C6-C—H...O(sulfoxide) and π(phthalazinone-N2C4)–π(phthalazinone-C6) stacking [inter-centroid distance = 3.5474 (9) Å] contacts lead to a linear supramolecular tape along the a-axis direction; tapes assemble without directional interactions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of the C—H...O and π-stacking interactions but, also H...H and C—H...C contacts. The calculation of the interaction energies indicate the importance of dispersion terms with the greatest energies calculated for the C—H...O and π-stacking interactions.

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.

, crystal structure, computational analysis and biological properties of 1-(4-chlorobenzoyl)-3-[2-(2-{2-[3-(4-chlorobenzoyl)-thioureido]-ethoxy}ethoxy)ethyl]thiourea and its Ni(II) and Cu(II) complexes

Lanthanide (Ln) compounds are common research targets in the field of magnetism and optics. Their properties arise from the electrons localized in the f-orbital. Moreover, the effect of the covalency between lanthanide and ligands on magnetism has attracted significant attention. We have provided insight into the Gd–Pt bond (of the heterometallic Ln-Pt complexes: {[Pt(PhSAc)4]Ln[(PhSAc)4Pt]} NEt4·2DMF (Ln = Y(0), La(1), Gd(2); PhSAc = thiobenzoate, NEt4 = tetraethylammonium)); single-crystal polarized X-ray absorption near edge structure (XANES) reveal the electronic states around metal ion, where spectra of Gd-LIII edges show the Gd–Pt direction has the highest covalency (less ionic) around Gd ion in 2. In addition, calculating natural bonding (NBO) analysis, natural population analysis (NPA), LOL, and atoms in molecules (AIM), ab initio calculations reveal the role of metallic and organic ligands in the electronic and magnetic properties of Ln complexes. The slow magnetization relaxation of the Gd complex, which has not been reported previously in the Pt–Gd–Pt system, was observed up to 45 K, the highest temperature reported to date among isolated Gd-complexes (frequency range: 0.1–10000 Hz).