Oxygen-Donor Metalloligands Induce Slow Magnetization Relaxation in Zero Field for a Cobalt(II) Complex with {CoO4} Motif.

Most 3d metal-based single-molecule magnets (SMMs) use N-ligands or ligands with even softer donors to impart a particular coordination geometry and increase the zero-field splitting parameter |D|, while complexes with hard O-donor ligands showing slow magnetization relaxation are rare. Here, we report that a diamagnetic NiII complex of a tetradentate ligand featuring two N-heterocyclic carbene and two alkoxide-O donors, [LO,ONi], can serve as a {O,O'}-chelating metalloligand to give a trinuclear complex [(LO,ONi)Co(LO,ONi)](OTf)2 (2) with an elongated tetrahedral {CoIIO4} core, D = -74.3 cm-1, and a spin reversal barrier Ueff = 86.9 cm-1 in the absence of an external dc field. The influence of diamagnetic NiII on the electronic structure of the {CoO4} unit in comparison to [Co(OPh)4]2- (A) has been probed with multireference ab initio calculations. These reveal a contrapolarizing effect of the NiII, which forms stronger metal-alkoxide bonds than the central CoII, inducing a change in ligand field splitting and a 5-fold increase in the magnetic anisotropy in 2 compared to A, with an easy magnetization axis along the Ni-Co-Ni vector. This demonstrates a strategy to enhance the SMM properties of 3d metal complexes with hard O-donors by modulating the ligand field character via the coordination of diamagnetic ions and the benefit of robust metalloligands in that regard.

Theoretical Magnetic Relaxation and Spin-Phonon Coupling Study in a Series of Molecular Engineering Designed Bridged Dysprosocenium Analogues.

A detailed computational study of hypothetical sandwich dysprosium double-decker complexes, bridged by various numbers of aliphatic linkers, was performed to evaluate the effect of the structural modifications on their ground-state magnetic sublevels and assess their potential as candidates for single-molecule magnets (SMMs). The molecular structures of seven complexes were optimized using the TPSSh functional, and the electronic structure and magnetic properties were investigated using the complete active space self-consistent field method (CASSCF). Estimates of the magnetic moment blocking barrier (Ueff) and blocking temperatures (TB) are reported. In addition, a new method based on computed derivatives of effective demagnetization barriers Ueff with respect to vibrational normal modes was introduced and applied to evaluate the impact of spin-phonon coupling on the SMM properties. On the basis of the computed parameters, we have identified promising candidates with properties superior to those of the existing single-molecule magnets.

Air-stable four-coordinate cobalt(ii) single-ion magnets: experimental and ab initio ligand field analyses of correlations between dihedral angles and magnetic anisotropy.

For single-ion magnets (SIMs), understanding the effects of the local coordination environment and ligand field on magnetic anisotropy is key to controlling their magnetic properties. Here we present a series of tetracoordinate cobalt(ii) complexes of the general formula [FL2Co]X2 (where FL is a bidentate diamido ligand) whose electron-withdrawing -C6F5 substituents confer stability under ambient conditions. Depending on the cations X, these complexes adopt structures with greatly varying dihedral twist angle δ between the N-Co-N' chelate planes in the solid state (48.0 to 89.2°). AC and DC field magnetic susceptibility measurements show this to translate into very different magnetic properties, the axial zero-field splitting (ZFS) parameter D ranging from -69 cm-1 to -143 cm-1 with substantial or negligible rhombic component E, respectively. A close to orthogonal arrangement of the two N,N'-chelating σ- and π-donor ligands at the Co(ii) ion is found to raise the energy barrier for magnetic relaxation to above 400 K. Multireference ab initio methods were employed to describe the complexes' electronic structures, and the results were analyzed within the framework of ab initio ligand field theory to probe the nature of the metal-ligand bonding and spin-orbit coupling. A relationship between the energy gaps of the first few electronic transitions and the ZFS was established, and the ZFS was correlated with the dihedral angle δ as well as with the metal-ligand bonding variations, viz. the two angular overlap parameters eσ and eπs. These findings not only give rise to a Co(ii) SIM showing open hysteresis up to 3.5 K at a sweep rate of 30 Oe s-1, but they also provide design guidelines for Co(ii) complexes with favorable SIM signatures or even switchable magnetic relaxation properties.

Exchange Interactions and Magnetic Properties of a Molecular Mn18 -Ring Complex.

[Mn3 O(OAc)7 (HOAc)]6 ⋅ x AcOH (x=6-9) represents a rare example of a compound containing molecular Mn18 -rings. These are formed by Mn3 (µ3 -O) subunits in which the high-spin Mn(III) centers are bridged by three pairs of acetate anions (AcO- ). An AcOH molecule coordinates to one of the Mn atoms leading to [Mn3 (µ3 -O)(µ2 -OAc)6 (AcOH)]-units, designated in short as Mn3 -units, that are interconnected by acetate anions via the other two Mn atoms to form Mn18 -rings. Magnetic measurements show weak ferromagnetic interactions between them that are suppressed in strong magnetic field. Quantum-chemical calculations on Mn3 model complexes using independently DFT and ab-initio multi reference methods (CASSCF/NEVPT2) show a correlation between the orientation of the pseudo-Jahn-Teller axes of pairs of Mn(III) magnetic centers and corresponding exchange coupling energies. Weak coupling between Mn3 -units within the Mn18 -ring allowed to simulate the magnetic susceptibility versus temperature dependence in terms of basically uncoupled magnetic moments of each Mn3 -unit within the ring.

On the Single-Molecule Magnetic Behavior of Linear Iron(I) Arylsilylamides.

The rational design of 3d-metal-based single-molecule magnets (SMM) requires a fundamental understanding of their intrinsic electronic and structural properties and how they translate into experimentally observable features. Here, we determined the magnetic properties of the linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] (L = -N(Dipp)SiMe3; crypt = 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosan). For the former, slow-relaxation of the magnetization with a spin reversal barrier of Ueff = 152 cm-1 as well as a closed-waist magnetic hysteresis and magnetic blocking below 2.5 K are observed. For the more linear [KFeL2], in which the potassium cation is encapsulated by the aryl substituents of the amide ligands, the relaxation barrier and the blocking temperature increase to Ueff = 184 cm-1 and TB = 4.5 K, respectively. The increase is rationalized by a more pronounced axial anisotropy in [KFeL2] determined by dc-SQUID magnetometry. The effective relaxation barrier of [KFeL2] is in agreement with the energy spacing between the ground and first-excited magnetic states, as obtained by field-dependent IR-spectroscopy (178 cm-1), magnetic measurements (208 cm-1), as well as theoretical analysis (212 cm-1). In comparison with the literature, the results show that magnetic coercivity in linear iron(I) silylamides is driven by the degree of linearity in conjunction with steric encumbrance, whereas the ligand symmetry is a marginal factor.

Comprehensive Studies of Magnetic Transitions and Spin-Phonon Couplings in the Tetrahedral Cobalt Complex Co(AsPh3)2I2.

A combination of inelastic neutron scattering (INS), far-IR magneto-spectroscopy (FIRMS), and Raman magneto-spectroscopy (RaMS) has been used to comprehensively probe magnetic excitations in Co(AsPh3)2I2 (1), a reported single-molecule magnet (SMM). With applied field, the magnetic zero-field splitting (ZFS) peak (2D') shifts to higher energies in each spectroscopy. INS placed the ZFS peak at 54 cm-1, as revealed by both variable-temperature (VT) and variable-magnetic-field data, giving results that agree well with those from both far-IR and Raman studies. Both FIRMS and RaMS also reveal the presence of multiple spin-phonon couplings as avoided crossings with neighboring phonons. Here, phonons refer to both intramolecular and lattice vibrations. The results constitute a rare case in which the spin-phonon couplings are observed with both Raman-active (g modes) and far-IR-active phonons (u modes; space group P21/c, no. 14, Z = 4 for 1). These couplings are fit using a simple avoided crossing model with coupling constants of ca. 1-2 cm-1. The combined spectroscopies accurately determine the magnetic excited level and the interaction of the magnetic excitation with phonon modes. Density functional theory (DFT) phonon calculations compare well with INS, allowing for the assignment of the modes and their symmetries. Electronic calculations elucidate the nature of ZFS in the complex. Features of different techniques to determine ZFS and other spin-Hamiltonian parameters in transition-metal complexes are summarized.

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr3+ Ions in Emeralds.

Herein, we study the electronic structure, energies, and vibronic structure of optical d-d transitions of Cr3+ ions doped in beryl (Be3Si6Al2O18:Cr3+, emerald). A computational protocol is developed that combines periodic density functional theory (for modeling of the bulk crystalline lattice of emerald) and the multireference configuration interaction complete active space self-consistent field method supplemented with n-electron valence second-order perturbation theory (for the calculation of the energy levels, wave functions, and spin-Hamiltonian and ligand-field parameters of the trigonal Cr3+ centers in the [CrO6]9- clusters embedded in an extended point charge field). Ligand-field parameters were extracted from mapping the effective ligand-field Hamiltonian onto the full many-particle Hamiltonian from one side and from a direct fit to energies of computed d-d transitions on the other side. These have been analyzed using ab initio ligand-field theory. The quality of the theoretical predictions is critically assessed through a detailed comparison with the available experimental data.

Effect of Spin-Orbit Coupling on Phonon-Mediated Magnetic Relaxation in a Series of Zero-Valent Vanadium, Niobium, and Tantalum Isocyanide Complexes.

Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp)6 (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin-phonon computations support the role of spin-orbit coupling in modulating spin-phonon relaxation. Our results provide experimental evidence that increasing magnetic anisotropy through spin-orbit coupling interactions leads to increased spin-vibronic relaxation, which is detrimental to long spin lifetime in paramagnetic molecules.

Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear ZnII FeIII FeIII FeIII ZnII Complex.

The first confacial pentaoctahedron comprised of transition metal ions namely ZnII FeIII A FeIII B FeIII A ZnII has been synthesized by using a dinucleating nonadentate ligand. The face-sharing bridging mode enforces short ZnII ⋅⋅⋅FeIII A and FeIII A ⋅⋅⋅FeIII B distances of 2.83 and 2.72 Å, respectively. Ab-initio CASSCF/NEVPT2 calculations provide significant negative zero-field splittings for FeIII A and FeIII B with |DA |>|DB | with the main component along the C3 axis. Hence, a spin-Hamiltonian comprised of anisotropic exchange, zero-field, and Zeeman term was employed. This allowed by following the boundary conditions from the theoretical results the simulation in a theory-guided parameter determination with Jxy =+0.37, Jz =-0.32, DA =-1.21, EA =-0.24, DB =-0.35, and EB =-0.01 cm-1 supported by simulations of high-field magnetic Mössbauer spectra recorded at 2 K. The weak but ferromagnetic FeIII A FeIII B interaction arises from the small bridging angle of 84.8° being at the switch from anti- to ferromagnetic for the face-sharing bridging mode.

Coexistence of Two Different Distorted Octahedral [MnF6 ]3- Sites in K3 [MnF6 ]: Manifestation in Spectroscopy and Magnetism.

As a consequence of the static Jahn-Teller effect of the 5 E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6 ]3- anions with two longer and four shorter Mn-F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3 [MnF6 ] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6 ]3- anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6 ]3- anions are present in K3 [MnF6 ]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations.

Strong Electronic and Magnetic Coupling in M4 (M = Ni, Cu) Clusters via Direct Orbital Interactions between Low-Coordinate Metal Centers.

We present an extensive study of tetranuclear transition-metal cluster compounds M4(NPtBu3)4 and [M4(NPtBu3)4][B(C6F5)4] (M = Ni, Cu; tBu = tert-butyl), which feature low-coordinate metal centers and direct metal-metal orbital overlap. X-ray diffraction, electrochemical, magnetic, spectroscopic, and computational analysis elucidate the nature of the bonding interactions in these clusters and the impact of these interactions on the electronic and magnetic properties. Direct orbital overlap results in strongly coupled, large-spin ground states in the [Ni4(NPtBu3)4]+/0 clusters and fully delocalized, spin-correlated electrons. Correlated electronic structure calculations confirm the presence of ferromagnetic ground states that arise from direct exchange between magnetic orbitals, and, in the case of the neutral cluster, itinerant electron magnetism similar to that in metallic ferromagnets. The cationic nickel cluster also possesses large magnetic anisotropy exemplified by a large, positive axial zero-field splitting parameter of D = +7.95 or +9.2 cm-1, as determined by magnetometry or electron paramagnetic resonance spectroscopy, respectively. The [Ni4(NPtBu3)4]+ cluster is also the first molecule with easy-plane magnetic anisotropy to exhibit zero-field slow magnetic relaxation, and under a small applied field, it exhibits relaxation exclusively through an Orbach mechanism with a spin relaxation barrier of 16 cm-1. The S = 1/2 complex [Cu4(NPtBu3)4]+ exhibits slow magnetic relaxation via a Raman process on the millisecond time scale, supporting the presence of slow relaxation via an Orbach process in the nickel analogue. Overall, this work highlights the unique electronic and magnetic properties that can be realized in metal clusters featuring direct metal-metal orbital interactions between low-coordinate metal centers.

Spin-chemical effects on intramolecular photoinduced charge transfer reactions in bisphenanthroline copper(i)-viologen dyad assemblies.

Two covalently linked donor-acceptor copper phenanthroline complexes (C-A dyads) of interest for solar energy conversion/storage schemes, [Cu(i)(Rphen(OMV)2 4+)2]9+ = RC+A4 8+ with RC+ = [Cu(i)Rphen2]+ involving 2,9-methyl (R = Me) or 2,9-phenyl (R = Ph)-phenanthroline ligands that are 5,6-disubstituted by 4-(n-butoxy) linked methylviologen electron acceptor groups (A2+ = OMV2+), have been synthesized and investigated via quantum chemical calculations and nanosecond laser flash spectroscopy in 1,2-difluorobenzene/methanol (dfb/MeOH) mixtures. Upon photoexcitation, charge transfer (CT) states RC2+A+A3 6+ are formed in less than one ns and decay by charge recombination on a time scale of 6-45 ns. The CT lifetime of RC2+A+A3 6+ has a strong dependence on MeOH solvent fraction when R = Me, but is unaffected if R = Ph. This solvent effect is due to coordination of MeOH solvent in MeC+A4 8+ (i.e. exciplex formation) allowed by conformational flattening of the ligand sphere, which cannot occur in PhC+A4 8+ having bulkier Phphen ligand framework. Interestingly, the decay time of the CT state increases for both species at low magnetic fields with a maximum increase of ca. 30% at ca. 150 mT, then decreases as the field is increased up to 1500 mT, the highest field investigated. This magnetic field effect (MFE) is due to magnetic modulation of the spin dynamics interconverting 3CT and 1CT states. A quantitative modeling according to the radical pair mechanism involving ab initio multireference calculations of the complexes revealed that the spin process is dominated by the effect of Cu hyperfine coupling. The external magnetic field suppresses the hyperfine coupling induced spin state mixing thereby lengthening the CT decay time. This effect is counteracted by the field dependent processes of T0-S mixing through the Δg-mechanism and by a local mode spin-orbit mechanism. Further, the maximum MFE is limited by a finite rate of direct recombination of 3CT states and the spin-rotational mechanism of spin relaxation. This study provides a first comprehensive characterization of Cu(ii)-complex spin chemistry and highlights how spin chemistry can be used to manipulate solar energy harvesting and storage materials.

Improvement of Ab Initio Ligand Field Theory by Means of Multistate Perturbation Theory.

Over the last few years, ab initio ligand field theory (AILFT) has evolved into an important tool for the extraction of ligand field models from ab initio calculations. The inclusion of dynamic correlation on top of complete active space self-consistent field (CASSCF) reference functions, which is important for accurate results, was so far realized at the level of second-order N-electron valence state perturbation theory (NEVPT2). In this work, we introduce two alternative methods for the inclusion of dynamic correlation into AILFT calculations, the second-order dynamic correlation dressed complete active space method (DCD-CAS(2)) and the Hermitian quasi-degenerate NEVPT2 (HQD-NEVPT2). These methods belong to the class of multistate perturbation theory approaches, which allow for the mixing of CASSCF states under the effect of dynamic correlation (state-mixing). The two new versions of AILFT were tested for a diverse set of transition-metal complexes. It was found that the multistate methods have, compared to NEVPT2, an AILFT fit with smaller root mean square deviations (rmsds) between ab initio and AILFT energies. A comparison of AILFT excitation energies with the experiment shows that for some systems, the agreement gets better at the multistate level because of the smaller rmsds. However, for some systems, the agreement gets worse, which could be attributed to a cancellation of errors at the NEVPT2 level that is partly removed at the multistate level. An investigation of trends in the extracted ligand field parameters shows that at the multistate level, the ligand field splitting Δ gets larger, whereas the Racah parameters B and C get smaller and larger, respectively. An investigation of the reasons for the observed improvement for octahedral CrIII halide complexes shows that the possibility of state-mixing relaxes constraints that are present at the NEVPT2 level and that keep Δ and B from following their individual preferences.

Dispersion Forces Drive the Formation of Uranium-Alkane Adducts.

Single-crystal cryogenic X-ray diffraction at 6 K, electron paramagnetic resonance spectroscopy, and correlated electronic structure calculations are combined to shed light on the nature of the metal-tris(aryloxide) and η2-H, C metal-alkane interactions in the [((t·BuArO)3tacn)UIII(Mecy-C6)]·(Mecy-C6) adduct. An analysis of the ligand field experienced by the uranium center using ab initio ligand field theory in combination with the angular overlap model yields rather unusual U-OArO and U-Ntacn bonding parameters for the metal-tris(aryloxide) interaction. These parameters are incompatible with the concept of σ and π metal-ligand overlap. For that reason, it is deduced that metal-ligand bonding in the [((t·BuArO)3tacn)UIII] moiety is predominantly ionic. The bonding interaction within the [((t·BuArO)3tacn)UIII] moiety is shown to be dispersive in nature and essentially supported by the upper-rim tBu groups of the (t·BuArO)3tacn3- ligand. Our findings indicate that the axial alkane molecule is held in place by the guest-host effect rather than direct metal-alkane ionic or covalent interactions.

Chemistry and Quantum Mechanics in 2019: Give Us Insight and Numbers.

This Perspective revisits Charles Coulson's famous statement from 1959 "give us insight not numbers" in which he pointed out that accurate computations and chemical understanding often do not go hand in hand. We argue that today, accurate wave function based first-principle calculations can be performed on large molecular systems, while tools are available to interpret the results of these calculations in chemical language. This leads us to modify Coulson's statement to "give us insight and numbers". Examples from organic, inorganic, organometallic and surface chemistry as well as molecular magnetism illustrate the points made.

Probing Magnetic Excitations in CoII Single-Molecule Magnets by Inelastic Neutron Scattering.

Co(acac)2(H2O)2 (1, acac = acetylacetonate), a transition metal complex ( S = 3 / 2 ), displays field-induced slow magnetic relaxation as a single-molecule magnet. For 1 and its isotopologues Co(acac)2(D2O)2 (1-d 4 ) and Co(acac-d 7)2(D2O)2 (1-d 18 ) in approximately D 4 h symmetry, zero-field splitting of the ground electronic state leads to two Kramers doublets (KDs): lower energy M S = ± 1 / 2 ϕ 1 , 2 and higher energy M S = ± 3 / 2 ϕ 3 , 4 states. This work employs inelastic neutron scattering (INS), a unique method to probe magnetic transitions, to probe different magnetic excitations in 1-d 4 and 1-d 18 . Direct-geometry, time-of-flight Disk-Chopper Spectrometer (DCS), with applied magnetic fields up to 10 T, has been used to study the intra-KD transition as a result of Zeeman splitting, M S = - 1 / 2   ϕ 1 → M S = + 1 / 2   ϕ 2 , in 1-d 18 . This is a rare study of the M S = - 1 / 2 → M S = + 1 / 2 excitation in transition metal complexes by INS. Indirect-geometry INS spectrometer VISION has been used to probe the inter-KD, ZFS transition, M S = ± 1 / 2 ϕ 1 , 2 → M S = ± 3 / 2 ( ϕ 3 , 4 ) in both 1-d 4 and 1-d 18 , by variable-temperature (VT) properties of this excitation. The INS spectra measured on VISION also give phonon features of the complexes that are well described by periodic DFT phonon calculations.

A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state.

Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe2ONaph)3)2 (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (d x 2 -y 2 , d xy )3(d xz , d yz )3(d z 2 )1 electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450-wave number magnetic excited state.

Challenges in Multireference Perturbation Theory for the Calculations of the g-Tensor of First-Row Transition-Metal Complexes.

In this article, we have studied 34 S = 1/2 complexes of first-row transition-metal complexes in d1, d5, d7, and d9 configurations in an attempt to determine the intrinsic accuracy of the scalar-relativistic complete active space self-consistent field (CASSCF) and N-electron valence perturbation theory (NEVPT2) methods, with respect to predicting molecular g-values. CASSCF calculations based on active spaces that contain only metal-based orbitals largely overestimate the g-values, compared to experiment and often fail to provide chemically meaningful results. Incorporation of dynamic correlation by means of the NEVPT2 method significantly improves the transition energies, with a typical error, relative to the experiment, of 2000-3000 cm-1. As a result, a lowering in the g-shift by almost an order of magnitude is obtained, relative to the CASSCF results. However, the g-shifts are still overestimated, compared to the experiment, since CASSCF leads to an overly ionic description of the metal-ligand bond and, hence, to spin-orbit coupling matrix elements that are too large. Inclusion of the double d-shell, along with appropriate bonding counterparts to the antibonding d-orbitals in the active space, led to the correct trends in the g-values for all studied complexes, with the linear regression coefficient ( R) equal to 0.93 over the entire dataset. Various technical aspects of the calculations such as the influence of relativity, importance of picture change effects, solvation effects, and comparison between second-order perturbation and effective Hamiltonian-based theories have also been systematically studied. In addition, g-tensor calculations were performed with five popular density functional theory (DFT) methods (B3LYP, M06L, M06, TPSSh, and PBE0) to compare with wave function (WF) methods. Our results suggest that WF-based methods are remarkably better than DFT methods. However, despite the fact that WF theory has come a long way in computing the properties of large, open-shell transition-metal complexes, methodological work is still necessary for truly high accuracies to be reached.

Spin-phonon couplings in transition metal complexes with slow magnetic relaxation.

Spin-phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1-2 cm-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin-phonon couplings in typical transition metal complexes and sheds light on the origin of the spin-phonon entanglement.

The [U2 F12 ]2- Anion of Sr[U2 F12 ].

The D2h -symmetric dinuclear complex anion [U2 F12 ]2- of pastel green Sr[U2 F12 ] shows a hitherto unknown structural feature: The coordination polyhedra around the U atoms are edge-linked monocapped trigonal prisms, the UV atoms are therefore seven-coordinated. This leads to a U-U distance of 3.8913(6) Å. A weak UV -UV interaction is observed for the dinuclear [U2 F12 ]2- complex and described by the antiferromagnetic exchange Jexp of circa -29.9 cm-1 . The crystalline compound can be easily prepared from SrF2 and ß-UF5 in anhydrous hydrogen fluoride (aHF) at room temperature. It was studied by means of single crystal X-ray diffraction, IR, Raman and UV/VIS spectroscopy, magnetic measurements, and by molecular as well as by solid-state quantum chemical calculations.