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Previously limited to highly symmetrical homoleptic triple‐helical complexes [Er(Lk)3]3+, where Lk are polyaromatic tridentate ligands, single‐center molecular‐based upconversion using linear optics and exploiting the excited‐state absorption mechanism (ESA) greatly benefits from the design of stable and low‐symmetrical [LkEr(hfa)3] heteroleptic adducts (hfa−=hexafluoroacetylacetonate anion). Depending on (i) the extended π‐electron delocalization, (ii) the flexibility and (iii) the heavy atom effect brought by the bound ligand Lk, the near‐infrared (801 nm) to visible green (542 nm) upconversion quantum yield measured for [LkEr(hfa)3] in solution at room temperature can be boosted by up to three orders of magnitude. [ABSTRACT FROM AUTHOR]

[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2‐pyridylmethyl)amine and Mesaldien=N,N'‐(2‐aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014, 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g‐factors of the monomers are interconnected. The central magnetic unit [UVO2]+ is described by a Kramers Doublet (KD) with negative g‐factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)‐U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component JZ twice larger as the perpendicular one J⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the JZ/J⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g‐factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding gS‐values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [UVO2]+ 5 f orbitals. [ABSTRACT FROM AUTHOR]

The compound [BiCNIm]3[DyCl6] was synthesized from a nitrile‐functionalized imidazolium ionic liquid [BiCNIm][Cl] and DyCl3 ⋅ 6H2O in acetonitrile using solvothermal conditions. Structural characterization reveals that the Dy3+ ions are in a quasi‐regular octahedral environment, formed by six chloride anions. The magnetic study indicates that this mononuclear compound exhibits a Single Ion Magnet behaviour. This behaviour is compared to that of other mononuclear compounds containing Dy3+ ions in various octahedral environment. [ABSTRACT FROM AUTHOR]

Actinide +VI complexes (AnVI =UVI , NpVI and PuVI) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, NpVI and PuVI complexes were described by first principles CAS based and two‐component spin‐restricted DFT methods. The analysis of the 1H paramagnetic NMR chemical shifts for all protons of the ligands according to the X‐rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans' method. The SO‐RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the NpVI complex. The temperature dependence of the pNMR chemical shifts has a strong 1/T contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two‐Kramers‐doublet model for the NpVI complex and a non‐Kramers‐doublet model for the PuVI complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center. [ABSTRACT FROM AUTHOR]

We report Peacock-Weakley complexes, Na9[Ln(W5O18)2].35H2O, formed with Tm(III), 1, and Yb(III), 2. Their syntheses, physico-chemical characterizations, crystal structures, and magnetic properties are described. Ab initio calculations are also reported. These polyoxometalate (POM) complexes were obtained using original synthetic conditions where acidification was performed with a stoichiometric amount of nitric acid to an acidity of Z = v(H+)/v(WO4²-) = 8/10 = 0.80. Both the Tm(III) and Yb(III) derivatives were found to exhibit field-induced slow relaxation of their magnetization likely controlled by Raman and Orbach relaxation processes. 1 is a rare example of a Tm(III)-based single-molecule magnet (SMM) and is a consequence of the oblate tetragonal anti-prismatic symmetry of the coordination sphere. [ABSTRACT FROM AUTHOR]

The triiodide ion I3- exhibits a complex photodissociation behavior, the dynamics of which are not yet fully understood. As a first step toward determining the full potential energy surfaces of this species for subsequent simulations of its dissociation processes, we investigate the performance of different electronic structure methods [time-dependent density functional theory, complete active space perturbation theory to second order (CASPT2), Fock-space coupled cluster and multireference configuration interaction] in describing the ground and excited states of the triiodide ion along the symmetrical dissociation path. All methods apart from CASPT2 include scalar relativity and spin-orbit coupling in the orbital optimization, providing useful benchmark data for the more common two-step approaches in which spin-orbit coupling is introduced in the configuration interaction. Time-dependent density functional theory with the statistical averaging of model orbital potential functional is off the mark for this system. Another choice of functional may improve performance with respect to vertical excitation energies and spectroscopic constants, but all functionals are likely to face instability problems away from the equilibrium region. The Fock-space coupled cluster method was shown to perform clearly best in regions not too far from equilibrium but is plagued by convergence problems toward the dissociation limit due to intruder states. CASPT2 shows good performance at significantly lower computational cost, but is quite sensitive to symmetry breaking. We furthermore observe spikes in the CASPT2 potential curves away from equilibrium, signaling intruder state problems that we were unable to curb through the use of level shifts. Multireference configuration interaction is, in principle, a viable option, but its computational cost in the present case prohibits use other than for benchmarking purposes. [ABSTRACT FROM AUTHOR]

The ground and first excited states of PaX62- (X=F,Cl,Br,I), UX6- (X=F,Cl,Br) and NpF6 are calculated using the spin-orbit complete active space perturbation theory at second order method and the g-factors are deduced. The isotropic g-matrix is built from first principles, and the g-factors are found to be negative. Results are analyzed in the frame of crystal field theory. It is shown that it is more appropriate to consider the spin-orbit coupling before the crystal field interaction and that g-factors are principally governed by the metal-ligand distance. The complexes of the series with the longest bond length, even with a high covalent character, exhibit g-factors close to the free ion value. [ABSTRACT FROM AUTHOR]

The ground and excited states of the AmO2+, AmO22+, and AmO23+ ions have been studied using the four-component configuration interaction singles doubles, spin-orbit complete active space self-consistent field, and spin-orbit complete active space-order perturbation theory methods. The roles of scalar relativistic effects and spin-orbit coupling are analyzed; results with different methods are carefully compared by a precise analysis of the wave functions. A molecular spinor diagram is used in relation to the four-component calculations while a ligand field model is used for the two-step method. States with the same number of electrons in the four nonbonding orbitals are in very good agreement with the two methods while ligand field and charge transfer states do not have the same excitation energies. [ABSTRACT FROM AUTHOR]

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16(picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3](C3H5N2)3⋅3H2O series (Ln=Ce–Yb; dpa=2,6‐dipicolinic acid) with approximate three‐fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many‐electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second‐order parameter B02 differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects. [ABSTRACT FROM AUTHOR]

The magnetic properties of LnIII and AnIII complexes formed with dipicolinate ligands have been studied by NMR spectroscopy. To know precisely the geometries of these complexes, a crystallographic study by single‐crystal X‐ray diffraction (XRD) and extended X‐ray absorption fine structure (EXAFS) in solution was performed. Several methods to separate the paramagnetic shifts observed in the NMR spectra were applied to these complexes. Methods using a number of nuclei of the dipicolinate ligands revealed an abrupt change in the geometries of the complexes and a metal–ligand interaction in the middle of the lanthanide series. A study of the variation of the paramagnetic shifts with temperature demonstrated that higher‐order terms of the dipolar and contact contributions are required, especially for the lightest LnIII and almost all the studied AnIII. Bleaney's parameters a and CaD relating to the contact and dipolar terms, respectively, were deduced from experimental data and compared with the results of ab initio calculations. Quite a good agreement was found for the temperature dependencies of a and CaD. However, the CaD values obtained from cation magnetic anisotropy calculations showed some discrepancies with the values derived from Bleaney's equation defined for LnIII. Other parameters, such as the crystal field parameter and the hyperfine constants Fi obtained from the experimental data of the [An(ethyl‐dpa)3]3− complexes (ethyl‐dpa=4‐ethyl‐2,6‐dipicolinic acid), are at odds with the assumptions underlying Bleaney's theory. Valid for Ln, but for An? Is Bleaney's equation for paramagnetic NMR shifts of LnIII valid for AnIII complexes? (see figure) Several methods have been applied to separate the paramagnetic shifts observed in the NMR spectra of LnIII and AnIII complexes formed with dipicolinate ligands. Discrepancies with Bleaney's equation have been found for the AnIII complexes, and some parameters are at odds with the assumptions underlying Bleaney's theory. [ABSTRACT FROM AUTHOR]

A theoretical framework for the generation of natural orbitals, natural spin orbitals, as well as orbital- and spin-magnetizations, from multi-configurational ab initio wavefunction calculations including spin-orbit coupling is presented. Selected case studies show how these computational orbital and magnetization tools can be used to interpret and rationalize the magnetic properties of complexes containing transition metals, lanthanides, and actinides. [ABSTRACT FROM AUTHOR]

Abstract: The flexibility of first‐principles (ab initio) calculations with the SO‐CASSCF (complete active space self‐consistent field theory with a treatment of the spin‐orbit (SO) coupling by state interaction) method is used to quantify the electrostatic and covalent contributions to crystal field parameters. Two types of systems are chosen for illustration: 1) The ionic and experimentally well‐characterized PrCl3 crystal; this study permits a revisitation of the partition of contributions proposed in the early days of crystal field theory; and 2) a series of sandwich molecules [Ln(ηn‐CnHn)2]q, with Ln=Dy, Ho, Er, and Tm and n=5, 6, and 8, in which the interaction between LnIII and the aromatic ligands is more difficult to describe within an electrostatic approach. It is shown that a model with three layers of charges reproduces the electrostatic field generated by the ligands and that the covalency plays a qualitative role. The one‐electron character of crystal field theory is discussed and shown to be valuable, although it is not completely quantitative. This permits a reduction of the many‐electron problem to a discussion of the energy of the seven 4f orbitals. [ABSTRACT FROM AUTHOR]

We present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl6− complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E5/2u and the MCD is a UGRAPHIC DISPLAY="INLINE" ID="UGT1" SRC="UGT1"/-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell, and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the UGRAPHIC DISPLAY="INLINE" ID="UGT2" SRC="UGT2"/-terms: Under Oh double group symmetry, E5/2u→ E5/2g transitions have negative UGRAPHIC DISPLAY="INLINE" ID="UGT3" SRC="UGT3"/-terms whereas E5/2u→ F3/2g transitions have positive UGRAPHIC DISPLAY="INLINE" ID="UGT4" SRC="UGT4"/-terms if the ground state g-factor is negative, as it is the case for UCl6−. [ABSTRACT FROM AUTHOR]

By using complementary experimental techniques and first-principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2 v, has been investigated. Four complexes have the general formula [Ni(bpy)X2] n+ (bpy=2,2′-bipyridine; X2=bpy ( 1), (NCS−)2 ( 2), C2O42− ( 3), NO3− ( 4)). In the fifth complex, [Ni(HIM2-py)2(NO3)]+ ( 5; HIM2-py=2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1 H-imidazolyl-1-hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2-py. Analysis of the high-field, high-frequency electronic paramagnetic resonance (HF-HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from −1 to −10 cm−1. First-principles SO-CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3, on one hand, and 4 and 5, on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters ( D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg-like orbitals and is due to the difference in the σ-donor strength of NO3− and bpy or HIM2-py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g-like orbitals; and 2) the anisotropy of complexes 1- 3 arises from the small splitting of the t2g-like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. [ABSTRACT FROM AUTHOR]

A novel ester-functionalized bi-compartmental Schiff-base ligand and its dinuclear Zn-Ln complexes [Ln = Dy ( 1), Tb ( 2), Gd ( 3)] are reported herein. Athough electron-withdrawing substituents at the para position of the phenol moieties do not change the coordination environment of the Ln centers in comparison with the nonfunctionalized ligand, they have a clear steric effect on the crystal packing and alter the coordination strength of the central ligand core. This is illustrated by the atypical reactivity of the bi-compartmental Schiff-base ligand towards Ln coordination and corroborated by its longer bond lengths to the rare-earth ions in comparison with the nonfunctionalized ligand. Crystal structures, magnetic behavior, and ab initio calculations for the two series of complexes are reported. A slow relaxation of the magnetization with an energy barrier of 96 K was found for Dy derivative 1 in zero field. [ABSTRACT FROM AUTHOR]

In a previous paper, the influence of radioactive decay (α and β−) on magnetic susceptibility measurements by the Evans method has been demonstrated by the study of two americium isotopes. To characterize more accurately this phenomenon and particularly its influence on the Curie law, a new study has been performed on two uranium isotopes (238U and 233U) and on tritiated water (3H2O). The results on the influence of α emissions have established a relationship between changes in the temperature dependence and the radioactivity in solution. Regarding the β− emissions, less influence was observed while no temperature dependence linked to this kind of radioactive emission could be identified. Once magnetic susceptibility measurements of actinide(iii) cations were corrected from radioactivity effects, methods of quantum chemistry have been used on free ions and aquo complexes to calculate the electronic structure explaining the magnetic properties of Pu(iii), Am(iii) and Cm(iii). The ligand field effect on the magnetic behavior (the Curie constant and temperature-independent susceptibilities) was analyzed by considering different solvation environments. [ABSTRACT FROM AUTHOR]

The electron densities associated with the Ln 4f shell, and spin and orbital magnetizations (‘magnetic moment densities’), are investigated for the Ln(COT)2− series. The densities are obtained from ab-initio calculations including spin–orbit coupling. For Ln = Ce, Pr the magnetizations are also derived from crystal field models and shown to agree with the ab-initio results. Analysis of magnetizations from ab-initio calculations may be useful in assisting research on single molecule magnets. [ABSTRACT FROM AUTHOR]

The electronic structure and magnetic properties of neptunyl(VI), NpO22+, and two neptunyl complexes, [NpO2(NO3)3]− and [NpO2Cl4]2−, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO2Cl4]2−, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. [ABSTRACT FROM AUTHOR]

Abstract: The magnetic properties of the octahedral cluster NpCl diluted in Cs2ZrCl6 crystal have been calculated using a first principle method, SO-CASPT2. The spin Hamiltonian parameters modeling the fourfold degenerate ground state are extracted from calculations according to a first principle procedure. The agreement with the model parameters issued from experimental EPR data is good. The spin and orbital contributions to the model parameters are evaluated. Calculations are compared to crystal field theory at the different steps of calculations: while this theory is a very good framework to explain the main magnetic behavior, it is shown that it is not able to render precisely all the small effects. [Copyright &y& Elsevier]

We investigate and compare the magnetic properties of two isostructural DyIII-containing complexes. The DyIII ions are chelated by hexadentate ligands and possess two apical bidendate nitrate anions. In dysprosium(III) N,N'-bis(imine-2-yl)methylene-1,8-diamino-3,6-dioxaoctane (1), the ligand's donor atoms are two alkoxo, two pyridine, and two imine nitrogen atoms. Dysprosium(III) N,N'-bis(amine-2-yl)methylene-1,8-diamino-3,6-dioxaoctane (2) is identical with 1 except for one modification: the two imine groups have been replaced by amine groups. This change has a minute effect on the structure and a larger effect the magnetic behavior. The two complexes possess slow relaxation of the magnetization in the presence of an applied field of 1000 Oe but with a larger barrier for reorientation of the magnetization for 1 (Ueff/kB = 50 K) than for 2 (Ueff/kB = 34 K). First-principles calculations using the spin-orbit complete active-space self-consistent-field method were performed and allowed to fit the experimental magnetization data. The calculations gave the energy spectrum of the 2J + 1 sublevels issued from the J = 15/2 free-ion ground state. The lowest-lying sublevels were found to have a large contribution of MJ = ±15/2 for 1, while for 2, MJ = ±13/2 was dominant. The observed differences were attributed to a synergistic effect between the electron density of the ligand and the small structural changes provoked by a slight alteration of the coordination environment. It was observed that the stronger ligand field (imine) resulted in complex 1 with a larger energy barrier for reorientation of the magnetization than 2. [ABSTRACT FROM AUTHOR]

The large antiferromagnetic coupling in the MnIV–MnIV bond in the Li6Ca2[Mn2N6] and Li6Sr2[Mn2N6] crystals (J = –739 and –478 cm–, respectively, with H = ...) is studied using different theoretical methods: solid-state density functional theory calculations, molecular density functional theory, and post-Hartree–Fock calculations with large embeddings. This magnetic coupling is a challenge for theoretical methods because both correlation and polarization effects are crucial for the correct description of the bond. All methods predict a large antiferromagnetic coupling, but none of the considered methods give a quantitative agreement with the experimental values. The molecular methods, except B3LYP and CASPT2, underestimate the coupling for the calcium compound, while they overestimate it in the strontium compound, within 30%. These methods, on the other hand, strongly underestimate the decrease of the coupling between the two compounds, with the most correlated one predicting the same value for both compounds. The solid-state method overestimates the coupling within 60% but reproduces better their ratio. Analysis of the calculations shows that the magnetic coupling between the local π orbitals is not caused by a direct interaction but by the spin-polarized σ bond. [ABSTRACT FROM AUTHOR]

The Creutz-Taube complex [(NH3)5-Ru-pyrazine-Ru-(NH3)5]5+ is studied using wave function-based methods, namely the CASSCF/MS-CASPT2 method. Spin-orbit effects have been calculated with the SO-RASSl program. The nature of the ground state is analyzed, and all the excited states up to 50 000 cm-1 are calculated. They form a quasi continuum from 25 000 cm-1, theoretical bands are assigned to UV-visible spectra, and MCD bands are assigned by calculating transition moments from first principles for both spectroscopies, g-Factors are calculated from first principles and modeled by a model Hamiltonian: they compare well to experimental values and are shown to be the same as in the monomeric species. [ABSTRACT FROM AUTHOR]