Building Molecular Nanomagnets by Encapsulating Lanthanide Ions in Boron Nitride Nanotubes: Investigation.

Lanthanide-based single-ion magnets have attracted much interest due to their great potential for information storage at the level of one molecule. Among various strategies to enhance magnetization blocking in such complexes, the synthesis of axially symmetric compounds is regarded as the most promising. Here, we investigate theoretically the magnetization blocking of several lanthanide ions (Tb, Dy, Ho, Er, and Tm) encapsulated in highly symmetric zigzag boron nitride nanotubes (BNNTs) of different diameters with methodology.

Increasing the Magnetic Blocking Temperature of Single-Molecule Magnets.

The synthesis of single-molecule magnets (SMMs), magnetic complexes capable of retaining magnetization blocking for a long time at elevated temperatures, has been a major concern for magnetochemists over the last three decades. In this review, we describe basic SMMs and the different approaches that allow high magnetization-blocking temperatures to be reached. We focus on the basic factors affecting magnetization blocking, magnetic axiality and the height of the blocking barrier, which can be used to group different families of complexes in terms of their SMM efficiency.

Single-ion magnet behavior of Ln encapsulated in carbon nanotubes: an insight.

Single-molecule magnets (SMMs) have attracted large interest owing to their capability to store information at the level of a single molecule, which has great potential for applications in information technology. The key characteristic required for SMM performance is the magnetization blocking barrier, and in the last decade, impressive efforts have been made to increase its height. Herein, we report an investigation of the SMM behavior of a series of lanthanide ions (Tb, Dy, Ho, Er, Tm and Yb) encapsulated in zigzag carbon nanotubes (CNTs) of different diameters.

The OpenMolcas : A Community-Driven Approach to Advancing Computational Chemistry.

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

A High-Performance Single-Molecule Magnet Utilizing Dianionic Aminoborolide Ligands.

The first example of a homoleptic f-block borolide sandwich complex is presented and shown to be a high-performance single-molecule magnet (SMM). The bis(borolide) complex [K(2.2.

Mechanisms of Luminescence in Lanthanide Complexes: A Crucial Role of Metal-Ligand Covalency.

A current understanding of the luminescence of lanthanide complexes is based on the phenomenological Judd-Ofelt (JO) theory. However, the mechanisms of electric-dipole transitions lying at its basis were never subjected to a rigorous analysis. Here, we investigate the contributions to the electric-dipole transitions in the ErS → I band of an erbium trensal complex using state-of-the-art calculations.

Toroidal centripetal arrangement of the magnetic moment in a Dy4 tetrahedron.

Magnetic investigation and calculations reveal toroidal arrangement of the magnetic moment rather than centripetal anisotropies in a tetrahedral Dy4 complex.

Towards understanding the magnetism of Os(IV) complexes: an insight.

The magnetism of a recently synthesized -[OsCl(κN-Hind)] complex (5d-system), where Hind = 2-indazole, was studied experimentally and theoretically. Relativistic CASSCF/CASPT2 calculations for this and model [OsCl] complexes were employed to understand the nature of the low-lying multiplets. It is found that despite strong metal-ligand covalency they are basically characterized by the total angular pseudo-momentum originating from the spin-orbit coupling of the ground-state spin = 1 with the orbital pseudo-momentum = 1 of the Os ion.

Isolation of a triplet benzene dianion.

Baird's rule predicts that molecules with 4n π electrons should be aromatic in the triplet state, but the realization of simple ring systems with such an electronic ground state has been stymied by these molecules' tendency to distort into structures bearing a large singlet-triplet gap. Here, we show that the elusive benzene diradical dianion can be stabilized through creation of a binucleating ligand that enforces a tightly constrained inverse sandwich structure and direct magnetic exchange coupling. Specifically, we report the compounds [K(18-crown-6)(THF)][M(BzN-Mes)] (M = Y, Gd; BzN-Mes = 1,3,5-tris[2',6'-(N-mesityl)dimethanamino-4'-tert-butylphenyl]benzene), which feature a trigonal ligand that binds one trivalent metal ion on each face of a central benzene dianion.

Holmium(iii) molecular nanomagnets for optical thermometry exploring the luminescence re-absorption effect.

Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores tunable anisotropy and the luminescence re-absorption effect of Ho complexes. Our concept is shown in dinuclear cyanido-bridged molecules, {[Ho(4-pyridone)(HO)][M(CN)]}·HO (M = Co, ; Rh, ; Ir, ) and their magnetically diluted analogues, {[Ho Y (4-pyridone)(HO)][M(CN)]}·HO (M = Co, = 0.

Modern quantum chemistry with [Open]Molcas.

MOLCAS/OpenMolcas is an ab initio electronic structure program providing a large set of computational methods from Hartree-Fock and density functional theory to various implementations of multiconfigurational theory. This article provides a comprehensive overview of the main features of the code, specifically reviewing the use of the code in previously reported chemical applications as well as more recent applications including the calculation of magnetic properties from optimized density matrix renormalization group wave functions.

Yu-Shiba-Rusinov bands in ferromagnetic superconducting diamond.

The combination of different exotic properties in materials paves the way for the emergence of their new potential applications. An example is the recently found coexistence of the mutually antagonistic ferromagnetism and superconductivity in hydrogenated boron-doped diamond, which promises to be an attractive system with which to explore unconventional physics. Here, we show the emergence of Yu-Shiba-Rusinov (YSR) bands with a spatial extent of tens of nanometers in ferromagnetic superconducting diamond using scanning tunneling spectroscopy.

Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy.

Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of Tb and Cd ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species.

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium- and Terbium-[1]Ruthenocenophane Complexes.

We report the first f-block-ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal-prismatic geometry stabilizes the magnetic ground state in the case of Dy and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb .

An Inconspicuous Six-Coordinate Neutral Dy Single-Ion Magnet with Remarkable Magnetic Anisotropy and Stability.

It is a crucial challenge to address both magnetic anisotropy and stability for single-molecule magnets (SMMs) used in next-generation nanodevices. Highly axial lanthanide SMMs with neutral charge and moderate coordination numbers represent promising magnetic materials. Here, using iodide ions with large volume and low surface charge density as weak donors, we report a six-coordinate neutral dysprosium SMM [Dy(CyPO)I(CHCN)] with a certain degree of stability exhibiting a huge thermal barrier of 1062 K and hysteresis loops open up to 9 K.

Magnetic Anisotropy in Divalent Lanthanide Compounds.

Complexes of trivalent lanthanides (Ln) are known to possess strong magnetic anisotropy, which enables them to be efficient single-molecule magnets. High-level ab initio calculations are reported for [LnO] (where Ln is terbium (Tb), dysprosium (Dy), or holmium (Ho)), which show that divalent lanthanides can exhibit equally strong magnetic anisotropy and magnetization blocking barriers. In particular, detailed calculations predict a multilevel magnetization blocking barrier exceeding 3000 K for a [DyO] complex deposited on a hexagonal boron nitride (h-BN) surface, bringing the expected performance of single-molecule magnets to a qualitatively new level compared to the current state-of-the art complexes.

Trends in trigonal prismatic Ln-[1]ferrocenophane complexes and discovery of a Ho single-molecule magnet.

Lanthanide metallocenophanes are an intriguing class of organometallic complexes that feature rare six-coordinate trigonal prismatic coordination environments of 4f elements with close intramolecular proximity to transition metal ions. Herein, we present a systematic study of the structural and magnetic properties of the ferrocenophanes, [LnFc(THF)Li], of the late trivalent lanthanide ions (Ln = Gd (), Ho (), Er (), Tm (), Yb (), Lu ()). One major structural trend within this class of complexes is the increasing diferrocenyl (Fc) average twist angle with decreasing ionic radius ( ) of the central Ln ion, resulting in the largest average Fc twist angles for the Lu compound .

Magnetization Dynamics and Coherent Spin Manipulation of a Propeller Gd(III) Complex with the Smallest Helicene Ligand.

A homoleptic gadolinium(III) complex with the smallest helicene-type ligand, 1,10-phenanthroline-,'-dioxide (phendo) [Gd(phendo)](NO)·MeOH (phendo = 1,10-phenanthroline-,'-dioxide, MeOH = methanol), shows slow relaxation of the magnetization characteristic for Single Ion Magnets (SIM), despite negligible magnetic anisotropy, confirmed by ab initio calculations. Solid state dilution magnetic and EPR studies reveal that the magnetization dynamics of the [Gd(phendo)] cation is controlled mainly by a Raman process. Pulsed EPR experiments demonstrate long phase memory times (up to 2.

OpenMolcas: From Source Code to Insight.

In this Article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform.

Correction: Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

[This corrects the article DOI: 10.1039/C8SC03170C.].

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy(bpm)(fod)] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry.

Single Crystal Investigations Unravel the Magnetic Anisotropy of the "Square-In Square" CrDy SMM Coordination Cluster.

In the search for new single molecule magnets (SMM), i.e., molecular systems that can retain their magnetization without the need to apply an external magnetic field, a successful strategy is to associate 3 and 4 ions to form molecular coordination clusters.

Anomalous transverse resistance in 122-type iron-based superconductors.

The study of transverse resistance of superconductors is essential to understand the transition to superconductivity. Here, we investigated the in-plane transverse resistance of BaKFeAs superconductors, based on ultra-thin micro-bridges fabricated from optimally doped single crystals. An anomalous transverse resistance was found at temperatures around the superconducting transition, although magnetic order or structure distortion are absent in the optimal doping case.

Effects of the Exchange Coupling on Dynamic Properties in a Series of CoGdCo Complexes.

Reaction of 2-hydroxy3-methoxybenzaldehyde ( o-vanillin) with 1,1,1-tris(aminomethyl)ethane, Me-C(CHNH), or with N, N', N''-trimethylphosphorothioic trihydrazide, P(S)[NMe-NH], yields two tripodal LH and LH ligands which are able to give cationic heterotrinuclear [LCoGdCoL] or [LCoGdCoL] complexes. The Co ions are coordinated to these deprotonated ligands in the inner NO site, while the Gd ion is linked to three deprotonated phenoxo oxygen atoms of two anionic [LCo] or [LCo] units. Air oxidation of these trinuclear complexes does not yield complexes associating Co and Gd ions.