Asymmetric [Dy2] molecules deposited into micro-SQUID susceptometers: characterization of their magnetic integrity.

The controlled integration of magnetic molecules into superconducting circuits is key to developing hybrid quantum devices. Herein, we study [Dy2] molecular dimers deposited into micro-SQUID susceptometers. The results of magnetic, heat capacity and magnetic resonance experiments, backed by theoretical calculations, show that each [Dy2] dimer fulfills the main requisites to encode a two-spin quantum processor.

Promoting exchange coupling in (Cp)GdX complexes.

Introducing magnetic coupling between lanthanide ions has been shown to yield better-performing single-molecule magnets (SMMs), as exemplified by the CpLnI family of compounds (Cp: pentaisopropylcyclopentadienyl, Ln: Gd, Tb, or Dy). This unique coupling is mediated through an unpaired electron hosted in a σ-like orbital, that results from the two 5d Ln ions, and understanding these interactions holds the key to continue advancing the rational design of SMMs. Here, we focus on the CpGdI spin-only system and apply a recently proposed DFT-based decomposition scheme to assess the chemical and structural factors that affect the magnetic coupling.

Computation of Magnetic Exchange Couplings in Photoexcited Systems Based on KS-DFT.

Many efforts have been made in the study of optically excited spin-coupled molecules due to their appealing features for quantum information sciences. However, the characterization of the magnetic exchange couplings occurring from the photoexcitation is challenging experimentally. In this context, theoretical determinations play a critical role and must provide evaluations with rigorous and cost-effective strategies.

Electronic Structure of a Neodymium(III) Tris(oxidiacetate) Complex from Luminescence Data and Ab Initio Calculations.

Neodymium(III) is a near-infrared emissive and magnetic ion, which has found use in various high-technology applications. Yet, accurate predictions of the luminescent and magnetic properties of neodymium(III) based on the coordination environment remain to be done. Guidelines exist, but to build structure-property relationships for this element, more data are needed.

Evaluation of Point Group Symmetry in Lanthanide(III) Complexes: A New Implementation of a Continuous Symmetry Operation Measure with Autonomous Assignment of the Principal Axis.

The structure of molecular systems dictates the physical properties, and symmetry is the determining factor for all electronic properties. This makes group theory a powerful tool in quantum mechanics to compute molecular properties. For inorganic compounds, the coordination geometry has been estimated as idealized polyhedra with high symmetry, which, through ligand field theory, provides predictive capabilities.

Temperature-dependent NIR-CPL spectra of chiral Yb(III) complexes.

Chiral, enantiopure Yb(III) complexes exhibit circularly polarized luminescence (CPL) in the near infrared (NIR) wavelength region. This CPL is quantified by the dissymmetry factor (). The excited state F consists of six m states degenerated in three Stark levels, due to the crystal-field splitting (CFS), which are populated in accordance with the Boltzmann distribution.

Tuning the slow magnetic relaxation with the substituents in anilate bridged bis(dysprosium) complexes.

Dinuclear lanthanide complexes [((HB(pz))Dy)(μ-ThAn)] (1Dy) and [((HB(pz))Dy)(μ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz) scorpionate capping ligand and anilate (An) bridging linkers, namely homosubstituted dithiophene- and heterosubstituted chlorocyanoanilate, bearing electron-donating and withdrawing substituents at the 3,6-positions of the benzoquinone core, are reported. 1Dy shows an octacoordinated {NO} Dy ion within a distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated Dy ion adopts a triangular dodecahedron geometry, while maintaining the same {NO} coordination sphere. Both complexes show field-induced single molecule magnet (SMM) behaviour, with tuning of the slow magnetic relaxation as a function of the nature of the substituents at the 3,6-positions of the anilate moiety.

Pressure-Induced Structural, Optical and Magnetic Modifications in Lanthanide Single-Molecule Magnets.

Lanthanide Single-Molecule Magnets are fascinating objects that break magnetic performance records with observable magnetic bistability at the boiling temperature of liquid nitrogen, paving the way for potential applications in high-density data storage. The switching of lanthanide SMM has been successfully achieved using several external stimuli such as redox reaction, pH titration, light irradiation or solvation/desolvation thanks to the high sensitivity of the magnetic anisotropy to any structural change in the lanthanide surrounding. Nevertheless, the use of applied high pressure as an external stimulus is largely underused, especially considering that it can be combined with high pressure X-ray diffraction to establish a complementary structure-property relationship.

What governs magnetic exchange couplings in radical-bridged dinuclear complexes?

Coupling transition metal or lanthanide ions through a radical bridging ligand is a promising route to increase performances in the area of single molecular magnets. A better understanding of the underlying physical mechanisms governing the magnetic exchange couplings is thus of valuable importance to design future compounds. Here, couplings in three series of metal-radical-metal compounds based on transition metal ions are investigated by means of the decomposition/recomposition methods.

investigations of circularly polarised luminescence in Samarium(III)-based complexes.

The present study aims to gain insight into the circularly polarised luminescence (CPL) of lanthanide complexes through the angle of one of their elements, namely Samarium. The simulation of luminescent properties of Samarium(III) complexes remains a challenge for computational chemistry, considering the multiconfigurational character of the electronic structure, the importance of the spin-orbit coupling and the fact that its emissive level is high in energy and preceded by numerous states of various multiplicity. Herein, a methodology based on CASSCF/RASSI-SO calculations is exposed and applied to simulate the CPL properties of two different Samarium(III) complexes, presenting either a rigid or a flexible architecture around the centre ion.

The resolution of the weak-exchange limit made rigorous, simple and general in binuclear complexes.

The correct interpretation of magnetic properties in the weak-exchange regime has remained a challenging task for several decades. In this regime, the effective exchange interaction between local spins is quite weak, of the same order of magnitude or smaller than the various anisotropic terms, which generates a complex set of levels characterized by spin mixing. Although the model multispin Hamiltonian in the absence of local orbital momentum, , is considered good enough to map the experimental energies at zero field and in the strong-exchange limit, theoretical works pointed out limitations of this simple model.

Threading a Linear Molecule Through a Macrocycle Thanks to Boron: Optical Properties of the Threaded Species and Synthesis of a Rotaxane.

Two BODIPYs and two boron β-diketonates were threaded through a macrocycle bearing a 2,2'-biphenol unit, showing thus the ability of boron to act as a gathering atom. The new threaded species were characterized by 1D and 2D NMR spectroscopy as well as by X-ray crystallography for one of them and their properties rationalized with quantum chemistry to unravel the vibronic contributions. The BODIPYs exhibited interesting fluorescence features with quantum yields up to 91 % and enhanced photostability compared to their non-threaded homologues.

Phospha-cyanines in Their Ideal Polymethine State: Synthesis and Structure-Property Relationships.

We report the synthesis and full characterization of a family of phosphorus-containing polymethine cyanines (phospha-cyanines). The compounds are easily prepared in two steps, starting from readily available phosphanes. The impact of the P-substituents and the counterions on the structural and optical properties is investigated through a joint experimental/theoretical approach.

Magneto-Chiral Dichroism in a One-Dimensional Assembly of Helical Dysprosium(III) Single-Molecule Magnets.

Here we report magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption of a chiral dysprosium(III) coordination polymer. The two enantiomers of [Dy(H6(py))(hfac)] [H6(py) = 2,15-bis(4-pyridyl)ethynylcarbo[6]helicene; hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate], where the chirality is provided by a functionalized helicene ligand, were structurally, spectroscopically, and magnetically investigated. Magnetic measurements reveal a slow relaxation of the magnetization, with differences between enantiopure and racemic systems rationalized on the basis of theoretical calculations.

Toroidal moment and dynamical control in luminescent 1D and 3D terbium calixarene compounds.

A toroidal moment can be generated spontaneously in inorganic (atom-based) ferrotoroidic materials that breaks both time-reversal and space-inversion symmetries, attracting great attention in solid-state chemistry and physics. In the field of molecular magnetism, it can also be achieved in lanthanide (Ln) involved metal-organic complexes usually with a wheel-shaped topological structure. Such complexes are called single-molecule toroics (SMTs), presenting unique advantages in spin chirality qubits and magnetoelectric coupling.

Isotopic enrichment in lanthanide coordination complexes: contribution to single-molecule magnets and spin qudit insights.

Lanthanide Single-Molecule Magnets (SMMs) fascinate the scientific community due to their plethora of potential applications ranging from data storage to spintronic devices and quantum computing. This review article proposes a comprehensive description of the influence of the nuclear spin, hyperfine interaction, on the magnetic properties of lanthanide SMMs and on quantum information processing of qudit. This influence is analysed for non-Kramers and Kramers lanthanide SMMs as well as for the electronic distribution of the electron in 4f orbitals oblate and prolate ions.

Tuning the Photophysical Properties of Aza-BODIPYs in the Near-Infrared Region by Introducing Electron-Donating Thiophene Substituents.

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis- and tetra-substituted azaboron-dipyrromethene (aza-BODIPY) dyes substituted by different electron donating groups connected to the aza-BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza-BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro-generated species.

Magnetic hysteresis and large coercivity in bisbenzimidazole radical-bridged dilanthanide complexes.

A judicious combination of radical ligands innate to diffuse spin orbitals with paramagnetic metal ions elicits strong magnetic exchange coupling which leads to properties important for future technologies. This metal-radical approach aids in effective magnetic communication of especially lanthanide ions as their 4f orbitals are contracted and not readily accessible. Notably, a high spin density on the donor atoms of the radical is required for strong coupling.

Tailored Lewis Acid Sites for High-Temperature Supported Single-Molecule Magnetism.

Generating or even retaining slow magnetic relaxation in surface immobilized single-molecule magnets (SMMs) from promising molecular precursors remains a great challenge. Illustrative examples are organolanthanide compounds that show promising SMM properties in molecular systems, though surface immobilization generally diminishes their magnetic performance. Here, we show how tailored Lewis acidic Al(III) sites on a silica surface enable generation of a material with SMM characteristics via chemisorption of (Cp)DyCl ((Cp) = 1,2,4-tri(-butyl)-cyclopentadienide).

Revisiting magnetic exchange couplings in heterodinuclear complexes through the decomposition method in KS-DFT.

Providing tools to understand the physical mechanisms governing magnetic properties in transition metal-based compounds is still of great interest. Here, the magnetic exchange coupling in a series of heterodinuclear complexes is investigated by means of the method. This work presents the first application of the method to systems where magnetic centres may bear more than one unpaired electron.

Intrinsically Switchable Electroactive Fluorophores Based on λ -Biphosphinines.

The synthesis and full characterization of a family of stable λ -biphosphinines connected in 4,4-position through a variety of π-conjugated bridges is reported. The impact of the π-bridge on the optical (absorption/emission) and redox properties was investigated using a joint experimental/theoretical approach. In contrast to the π-extended ones, the λ -biphosphinines directly connected through a C-C bond in 4,4-position display two easily accessible and reversible oxidations highlighting their multi-stage redox character.

Reversible Pressure-Magnetic Modulation in a Tetrathiafulvalene-Based Dyad Piezochromic Dysprosium Single-Molecule Magnet.

The extreme sensitivity of trivalent lanthanide ions to crystal field variations led to the emergence of single-molecule magnetic switching under various stimuli. The use of pressure as an external stimulus instead of classic light irradiation, oxidation or any chemical reactions allows a fine tuning of the magnetic modulation. Here the well-known pure isotopically enriched [ Dy(tta) (L)]⋅C H ( Dy) Single-Molecule Magnet (SMM) (tta =2-2-thenoyltrifluoroacetonate and L=4,5-bis(propylthio)-tetrathiafulvalene-2-(2-pyridyl)benzimidazole-methyl-2-pyridine) was experimentally investigated by single-crystal diffraction and squid magnetometry under high applied pressures.

A photochromic metallacycle with highly anisotropic Dy-F magnetic units.

A dinuclear metallacycle assembled from a bispyridyl dithienylethene linker and a highly anisotropic dysprosium based Single Molecule Magnet (SMM) shows magnetic hysteresis at 1.8 K together with photoisomerization in single crystals (SC). The impact of photoswitching on the SMM behavior is evidenced and related to the specific organization of the magnetic units.