Splitting Parameters Research Articles

Limitations on the D-Parameter in Ni(II) Complexes.

A number of hexacoordinate, pentacoordinate, and tetracoordinate Ni(II) complexes have been investigated by applying ab initio CASSCF + NEVPT2 + SOC calculations and Generalized Crystal Field Theory. The geometry of the coordination polyhedron covers D4h, D3h, D2h, D2d, C4v, C3v, and C2v symmetry. The calculated spin-Hamiltonian parameters D and E were compared to the available experimental data. The limiting values of the D-parameter in the class of Ni(II) complexes are identified. Magnetic anisotropy in Ni(II) complexes, expressed by the axial zero-field splitting parameter D, seriously depends upon the ground and first excited electronic states. In hexacoordinate complexes, the ground electronic term is nondegenerate 3B1g for the D4h symmetry; D is slightly positive or negative. In tetracoordinate systems, D is only positive when the electronic ground state is nondegenerate 3A or 3B; this diverges on the τ4 path when oblate bisphenoid approaches the prolate geometry and a level crossing with 3E occurs. In pentacoordinate systems, D could be extremely negative when approaching a trigonal bipyramid (Addison index τ5 ∼ 1, ground state 3E″). In pentacoordinate Ni(II) complexes with the D3h and C3v symmetry of the coordination polyhedron, the ground electronic term is orbitally doubly degenerate which causes the D-parameter stays undefined. It is emphasized that one has to inspect compositions of the spin-orbit multiplets from the spin states |MS⟩ and check whether the weights confirm the expected spin-Hamiltonian picture: with D > 0, the ground state contains a dominant part of |0⟩ (close to 100%) whereas with D < 0 the spin-orbit doublet is formed of |±1⟩ with high weights (approaching 50 + 50%). The calculations show that the situations are not black and white, and the mixing of the states might be more complex especially when the rhombic zero-field splitting parameter E is in the play. In the case of the 3E ground term, six spin-orbit multiplets are formed by mixing six |MS⟩ states from the ground and quasi-degenerate excited states.

Preparation of Xanthene-TEMPO Dyads: Synthesis and Study of the Radical Enhanced Intersystem Crossing.

We prepared a rhodamine-TEMPO chromophore-radical dyad (RB-TEMPO) to study the radical enhanced intersystem crossing (REISC). The visible light-harvesting chromophore rhodamine is connected with the TEMPO (a nitroxide radical) via a C-N bond. The UV-vis absorption spectrum indicates negligible electron interaction between the two units at the ground state. Interestingly, the fluorescence of the rhodamine moiety is strongly quenched in RB-TEMPO, and the fluorescence lifetime of the rhodamine moiety is shortened to 0.29 ns, from the lifetime of 3.17 ns. We attribute this quenching effect to the intramolecular electron spin-spin interaction between the nitroxide radical and the photoexcited rhodamine chromophore. Nanosecond transient absorption spectra confirm the REISC in RB-TEMPO, indicated by the detection of the rhodamine chromophore triplet excited state; the lifetime was determined as 128 ns, which is shorter than the native rhodamine triplet state lifetime (0.58 μs). The zero-field splitting (ZFS) parameters of the triplet state of the chromophore were determined with the pulsed laser excited time-resolved electron paramagnetic resonance (TREPR) spectra. RB-TEMPO was used as a photoinitiator for the photopolymerization of pentaerythritol triacrylate (PETA). These studies are useful for the design of heavy atom-free triplet photosensitizers, the study of the ISC, and the electron spin dynamics of the radical-chromophore systems upon photoexcitation.

Temperature Sensitivity of 14N-V and 15N-V Ground-State Manifolds.

We measure electron- and nuclear-spin transition frequencies in the ground state of nitrogen-vacancy (N-V) centers in diamond for two nitrogen isotopes (14N-V and 15N-V) over temperatures ranging from 77 to 400 K. Measurements are performed using Ramsey interferometry and direct optical readout of the nuclear and electron spins. We extract coupling parameters Q (for 14N-V), D, A‖, A⊥, and , and their temperature dependences for both isotopes. The temperature dependences of the nuclear-spin transitions within the spin manifold near room temperature are found to be 0.52(1) ppm/K for 14N-V(|mI = -1⟩ ↔ |mI = +1⟩) and -1.1(1) ppm/K for 15N-V(|mI = -1/2⟩ ↔ |mI = +1/2⟩). An isotopic shift in the zero-field splitting parameter D between 14N-V and 15N-V is measured to be ~ 120 kHz. Residual transverse magnetic fields are observed to shift the nuclear-spin transition frequencies, especially for 15N-V. We have precisely determined the set of parameters relevant for the development of nuclear-spin-based diamond quantum sensors with greatly reduced sensitivity to environmental factors.

Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate.

High-valent iron species have been implicated as key intermediates in catalytic oxidation reactions, both in biological and synthetic systems. Many heteroleptic Fe(IV) complexes have now been prepared and characterized, especially using strongly π-donating oxo, imido, or nitrido ligands. On the other hand, homoleptic examples are scarce. Herein, we investigate the redox chemistry of iron complexes of the dianonic tris-skatylmethylphosphonium (TSMP2-) scorpionate ligand. One-electron oxidation of the tetrahedral, bis-ligated [(TSMP)2FeII]2- leads to the octahedral [(TSMP)2FeIII]-. The latter undergoes thermal spin-cross-over both in the solid state and solution, which we characterize using superconducting quantum inference device (SQUID), Evans method, and paramagnetic nuclear magnetic resonance spectroscopy. Furthermore, [(TSMP)2FeIII]- can be reversibly oxidized to the stable high-valent [(TSMP)2FeIV]0 complex. We use a variety of electrochemical, spectroscopic, and computational techniques as well as SQUID magnetometry to establish a triplet (S = 1) ground state with a metal-centered oxidation and little spin delocalization on the ligand. The complex also has a fairly isotropic g-tensor (giso = 1.97) combined with a positive zero-field splitting (ZFS) parameter D (+19.1 cm-1) and very low rhombicity, in agreement with quantum chemical calculations. This thorough spectroscopic characterization contributes to a general understanding of octahedral Fe(IV) complexes.

The electronic structure and dynamics of the excited triplet state of octaethylaluminum(III)-porphyrin investigated with advanced EPR methods

The photoexcited triplet state of octaethylaluminum(III)-porphyrin (AlOEP) was investigated by time-resolved Electron Paramagnetic Resonance, Electron Nuclear Double Resonance and Electron Spin Echo Envelope Modulation in an organic glass at 10 and 80 K. This main group element porphyrin is unusual because the metal has a small ionic radius and is six-coordinate with axial covalent and coordination bonds. It is not known whether triplet state dynamics influence its magnetic resonance properties as has been observed for some transition metal porphyrins. Together with density functional theory modelling, the magnetic resonance data of AlOEP allow the temperature dependence of the zero-field splitting (ZFS) parameters, D and E, and the proton AZZ hyperfine coupling (hfc) tensor components of the methine protons, in the zero-field splitting frame to be determined. The results provide evidence that the ZFS, hfc and spin–lattice relaxation are indeed influenced by the presence of a dynamic process that is discussed in terms of Jahn-Teller dynamic effects. Thus, these effects should be taken into account when interpreting EPR data from larger complexes containing AlOEP.

Generation and Characterization of a Tetraradical Embedded in a Curved Cyclic Paraphenylene Unit.

Unique spin-spin (magnetic) interactions, ring-size effects on ground-state spin multiplicity, and in-plane aromaticity has been found in localized 1,3-diradicals embedded in curved benzene structures such as cycloparaphenylene (CPP). In this study, we characterized the magnetic interactions in a tetraradical consisting of two localized 1,3-diradical units connected by p-quaterphenyl within a curved CPP skeleton by electron paramagnetic resonance (EPR) spectroscopy and quantum chemical calculations. Persistent triplet species with zero-field splitting parameters similar to those of a triplet 1,3-diphenylcyclopentane-1,3-diyl diradical were observed by continuous wave (CW) or pulsed X-band EPR measurements. The quintet state derived from the ferromagnetic interaction between the two triplet diradical moieties was not detected at 20 K under glassy matrix conditions. At the B3LYP/6-31G(d) level of theory, the singlet state was lower in energy than the triplet and quintet states. These findings will aid in the development of open-shell species for material science application.

Environmental impacts of La2O3 on the optical and ligand field parameters of Ni ions inside Na2O-B2O3 glass

In this work, a glass system of La2O3, NiO, and Na2O borate glass was prepared by changing the concentrations of La2O3/B2O3 contents. Further, the internal structure, optical absorbance, and ligand field parameters of Ni ions were studied. The internal structure was investigated using the Fourier transform infrared technique. The optical absorbance was measured, and the optical band gaps were obtained using Tauc's plot. According to the internal structure studies, BO4 contents increase with increasing La2O3/B2O3 concentrations, while BO3 contents decrease. Furthermore, the brown color and the absorption band at 424–428 nm of the prepared glass samples confirm the existence of Ni2+ cations in the form of NiO4 species and they act as glass formers. Additionally, the observed bands at 424–428, 490–500 and 798–806 nm are associated with the spin-allowed electron transitions of Ni2+ in octahedral coordination. Furthermore, the observed bands at 710–718 and 940–950 nm are related to the electronic transitions for Ni2+ in tetrahedral coordination. Moreover, the positions of all absorption bands shift toward higher wavelengths (redshift) with higher La2O3 concentrations. Additionally, the fundamental glass absorption edges move toward lower energy values as La2O3/B2O3 contents increase, confirming the band gaps behavior. Also, with increasing La2O3/B2O3 contents, the linear and nonlinear refractive indices increase. These behaviors were justified by the optical basicity and the electronic polarizability increase. On the other hand, the ligand field parameters of Ni ions; the crystal field splitting and Racah parameters (B and C), show opposite behaviors with further La2O3 additions. In detail, the crystal field splitting shows decreasing values and Racah parameters show increasing values. These results reflect the tendency of the bonds between the Ni cations and their surroundings towards a higher ionic nature (lower covalent nature).

Probing the Influence of Structural Distortion and Axial Ligands on Magnetic Anisotropy in a Series of Chiral Pentagonal Bipyramidal Co(II) and Ni(II) Complexes

A series of magnetically anisotropic chiral pentagonal bipyramidal (PBP) Co(II) and Ni(II) complexes are prepared by employing chiral bis-hydrazone ligands, viz., 2,6-diacetylpyridinebis(R/S-lactic acid hydrazide) (R,R/S,S-daplh) and (R)/(S)-2, 6-diacetylpyridinebis(3-hydroxyisobutyric acid hydrazide) (R,R/S,S-daphibh). Investigations of magnetic anisotropy by wave function based ab initio CASSCF calculations manifest the presence of substantial negative uniaxial magnetic anisotropy in the present PBP Ni(II) complexes, while the chiral PBP Co(II) complexes display large easy-plane magnetic anisotropy. Magnetostructural correlations show the profound influence of structural distortions and the ligand field environment on the axial zero field splitting parameter (D). Accordingly, a convenient strategy to enhance the D parameter in PBP Co(II) and Ni(II) complexes is devised.

Geometrical isomerism in Ru2Au heterometal assembly: cis-linking of tetracyanidoaurate to tetrakis(μ-butanoato)diruthenium

A heterometal assembled complex of tetrakis(μ-butanoato)diruthenium(II,III) and tetracyanidoaurate(III) [RuIIRuIII(n-C3H7COO)4AuIII(CN)4]n was synthesized and characterized by the elemental analysis and infrared spectroscopy. The single-crystal X-ray structure analysis revealed that the complex consists of zigzag chain molecules of alternating arrangement of the Ru2(n-C3H7COO)4+ and Au(CN)4– units with cis-bridging mode of the Au(CN)4– units. The temperature dependence of the magnetic susceptibility data (4.5—300 K) showed that the magnetic interaction between the dinuclear RuIIRuIII units (S= 3/2) is negligibly small with a zero-field splitting parameter D value of 60 cm-1.

Enhanced Secure Communication via Novel Double-Faced Active RIS

Although the reconfigurable intelligent surface (RIS) technology is envisioned promising to enhance communication from all aspects, including physical-layer security, increasing concerns have lately been cast onto its defects—the severe “double-fading” loss and its confined-to-half-space coverage. Diverse novel RIS architectures have recently emerged to partially overcome these shortcomings, yet perfect solution is still absent. This paper proposes a novel double-faced active (DFA)-RIS structure to surmount the above two prominent defects simultaneously. Furthermore, we utilize the DFA-RIS to promote secrecy performance via jointly designing access point (AP)’s beamforming and DFA-RIS configuration towards maximizing sum secrecy rate (SR). The optimization problem is highly challenging due to the constraints deriving from the DFA-RIS architecture, especially the presence of power splitting parameters. By leveraging majorization–minimization (MM) and penalty dual decomposition (PDD) methods, we develop an efficient solution that updates all variables via convex optimization techniques. Our proposed solution is significant and general as it is applicable to all other cutting-the-edge RIS architectures to maximize sum SR, which has not yet been thoroughly worked out. Numerical results verify the convergence and effectiveness of our proposed algorithm and demonstrate that our proposed DFA-RIS architecture outperforms all other state-of-the-art RIS techniques to enhance communication security.

Nonlinear Cauchy/Robin inverse problems solved by an optimal splitting-linearizing method

In the paper we develop a novel optimal splitting-linearizing method (OSLM) to iteratively solve a nonlinear inverse Cauchy problem in a simply-connected domain. The nonlinear term in the nonlinear elliptic equation is decomposed at two sides through a splitting parameter, which is then linearized around the value at the previous iteration step. The multiple-scale Pascal-polynomial method together with the OSLM is employed to solve the Cauchy problem, of which the optimal value of the splitting parameter is achieved by minimizing a theoretic merit function. Then, we solve the Cauchy/Robin inverse problem of a nonlinear elliptic equation in a doubly-connected domain for recovering the unknown Cauchy data and Robin transfer coefficient on an inner boundary. Two-parameter bases are derived to automatically satisfy the prescribed Cauchy boundary conditions on the outer boundary. When the solution is convergent after solving a sequence of linear systems, one can retrieve the Cauchy data very accurately. Simultaneously, the unknown Robin transfer coefficient is recovered from a given convective boundary condition on the inner boundary by either a division method or a linear system method. To overcome the ill-posed property of Cauchy/Robin problems, the optimal splitting parameter and a scaling factor play the role as regularization parameters. These methods assembled are new techniques to solve the Cauchy/Robin inverse problems. Although a few overspecified data are merely given on the outer boundary, the novel method is quite accurate, robust against large noise, and is convergent very fast to find the entire solution, the Cauchy data and the Robin transfer coefficient. We assess the convergence by the computed order of convergence (COC) of the proposed iterative algorithms.

Chlorophyll triplet states in thylakoid membranes of Acaryochloris marina. Evidence for a triplet state sitting on the photosystem I primary donor populated by intersystem crossing.

Photo-induced triplet states in the thylakoid membranes isolated from the cyanobacterium Acaryocholoris marina, that harbours Chlorophyll (Chl) d as its main chromophore, have been investigated by Optically Detected Magnetic Resonance (ODMR) and time-resolved Electron Paramagnetic Resonance (TR-EPR). Thylakoids were subjected to treatments aimed at poising the redox state of the terminal electron transfer acceptors and donors of Photosystem II (PSII) and Photosystem I (PSI), respectively. Under ambient redox conditions, four Chl d triplet populations were detectable, identifiable by their characteristic zero field splitting parameters, after deconvolution of the Fluorescence Detected Magnetic Resonance (FDMR) spectra. Illumination in the presence of the redox mediator N,N,N',N'-Tetramethyl-p-phenylenediamine (TMPD) and sodium ascorbate at room temperature led to a redistribution of the triplet populations, with T3 (|D|= 0.0245cm-1, |E|= 0.0042cm-1) becoming dominant and increasing in intensity with respect to untreated samples. A second triplet population (T4, |D|= 0.0248cm-1, |E|= 0.0040cm-1) having an intensity ratio of about 1:4 with respect to T3 was also detectable after illumination in the presence of TMPD and ascorbate. The microwave-induced Triplet-minus-Singlet spectrum acquired at the maximum of the |D|-|E| transition (610MHz) displays a broad minimum at 740nm, accompanied by a set of complex spectral features that overall resemble, despite showing further fine spectral structure, the previously reported Triplet-minus-Singlet spectrum attributed to the recombination triplet of PSI reaction centre, [Schenderlein M, Çetin M, Barber J, et al. Spectroscopic studies of the chlorophyll d containing photosystem I from the cyanobacterium Acaryochloris marina. Biochim Biophys Acta 1777:1400-1408]. However, TR-EPR experiments indicate that this triplet displays an eaeaea electron spin polarisation pattern which is characteristic of triplet sublevels populated by intersystem crossing rather than recombination, for which an aeeaae polarisation pattern is expected instead. It is proposed that the observed triplet, which leads to the bleaching of the P740 singlet state, sits on the PSI reaction centre.

Testing observables for teleseismic shear-wave splitting inversions: ambiguities of intensities, parameters, and waveforms

We assess the capabilities of different observables for the inversion of core-refracted shear waves (XKS phases) to uniquely resolve the anisotropic structure of the upper mantle. For this purpose, we perform full-waveform calculations for relatively simple, canonical models of upper-mantle anisotropy. The models are characterized by two and four domains of different anisotropic properties. Specifically, we assume hexagonal symmetry with arbitrarily chosen strength of the anisotropy and orientation of the horizontal fast axis. XKS waveforms, generated from plane-wave initial conditions, traverse through anisotropic models and are recorded at the surface by a single station (in case of vertical variations) and by a dense station profile across the laterally and vertically varying structure. In addition to waveforms, we consider the effects of anisotropic variations on apparent splitting parameters and splitting intensity. The results show that, generally, it is not possible to fully resolve the anisotropic parameters of a given model, even if complete waveforms (under noisefree conditions and for the complete azimuthal range) are considered. This is because waveforms for significantly different anisotropic models can be indistinguishable. However, inversions of both waveforms and apparent splitting parameters lead to similar models that exhibit systematic variations of anisotropic parameters. These characteristics may be exploited to better constrain the inversions. The results also show that splitting intensity holds some significant drawbacks: First, even from measurements over a wide range of back-azimuth, there is no characteristic signature that would indicate depth variations of anisotropy. Secondly, identical azimuthal variations of splitting intensity for different anisotropic structures do not imply that the corresponding split waveforms are also similar. Thus, fitting of observed and calculated splitting intensities could lead to anisotropic models that are incompatible with the observed waveforms. We conclude that (bandlimited) XKS-splitting inversions and related tomographic schemes, even if based on complete waveforms, are not sufficient to fully resolve the heterogeneous anisotropic structures of the upper mantle and that combinations with alternative methods, based on e.g., receiver-function splitting, P-wave travel-time deviations, or surface waves, are required.

Monitoring the Local Structure and Magnetic Properties of the Dinuclear Cu2-Paddle Wheel Nodes in the Mesoporous Metal–Organic Framework, DUT-49(Cu), upon Adsorption-Induced Breathing Transitions

DUT-49(Cu) is a well-studied representative of flexible mesoporous frameworks, in particular, famous for long-lived overloaded metastable states in the presence of a variety of gases at defined temperatures, leading to “negative gas adsorption” transitions. Important mechanistic insights into these transitions in DUT-49 were obtained via in situ powder X-ray diffraction (PXRD) studies conducted in parallel to gas physisorption. However, for strongly X-ray absorbing probe molecules, such as xenon, such studies are not feasible, even if synchrotron radiation is used. Here we employ in situ electron paramagnetic resonance spectroscopy (EPR), PXRD, and adsorption isotherm measurements to explore the phase transformations in DUT-49(Cu) in the presence of xenon and compare its properties with the corresponding adsorption/desorption behavior of ethylene for this material. The antiferromagnetically coupled CuII–CuII dimers in the paddle-wheel (PW) units of this pillared layer MOF serve as local magnetic probes in the in situ EPR measurement. These experiments allowed us to monitor the op ↔ cp phase transformations during the xenon physisorption through the structural changes at the PW units encoded in the zero-field splitting parameters of the S = 1 state of the CuII dimers. The EPR data indicates an expansion of the unit cell for the cp phase in the presence of xenon. This novel EPR-derived insight into the phase transformation phenomena of the xenon-loaded DUT-49(Cu) could be validated by combined in situ EPR, PRXD, and adsorption isotherm measurements for ethylene adsorption over the same MOF material in a comparable temperature range.

Search for Toroidal Ground State and Magnetoelectric Effects in Molecular Spin Triangles with Antiferromagnetic Exchange

Using first-principles methods and spin models, we investigate the magnetic properties of transition-metal trimers Cr3 and Cu3. We calculate exchange coupling constants and zero-field splitting parameters using density functional theory and, with these parameters, determine the ground spin state as well as thermodynamic properties via spin models. Results for Cr3 indicate uniaxial magnetic anisotropy with a magnetic easy axis aligned along the 3-fold rotational symmetry axis and a mostly isotropic exchange interaction. The Cu3 molecule lacks rotational symmetry and our results show strong antisymmetric interactions for three distinct exchange couplings within the molecule. We are able to reproduce experimental findings on magnetic susceptibility and magnetization of Cr3 with the first-principles spin-Hamiltonian parameters. Our results show no presence of a toroidal ordering of spins for Cr3 and a finite toroidal moment for Cu3 in the ground state. We apply an external electric field up to 0.08 V/Å to each system to reveal the field dependence of exchange coupling as magnetoelectric effects. Finally, we scan the parameter space of a spin Hamiltonian to gain insights into which parameters would lead to a sizable toroidal moment in such systems.

Frequency swept pulses for the enhanced resolution of ENDOR spectra detecting on higher spin transitions of Gd(III)

Half-Integer High Spin (HIHS) systems with zero-field splitting (ZFS) parameters below 1 GHz are generally dominated by the spin |─1/2>→|+1/2 > central transition (CT). Accordingly, most pulsed Electron Paramagnetic Resonance (EPR) experiments are performed at this position for maximum sensitivity. However, in certain cases it can be desirable to detect higher spin transitions away from the CT in such systems. Here, we describe the use of frequency swept Wideband, Uniform Rate, Smooth Truncation (WURST) pulses for transferring spin population from the CT, and other transitions, of Gd(III) to the neighbouring higher spin transition |─3/2>→|─1/2 > at Q- and W-band frequencies. Specifically, we demonstrate this approach to enhance the sensitivity of 1H Mims Electron-Nuclear Double Resonance (ENDOR) measurements on two model Gd(III) aryl substituted 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) complexes, focusing on transitions other than the CT. We show that an enhancement factor greater than 2 is obtained for both complexes at Q- and W-band frequencies by the application of two polarising pulses prior to the ENDOR sequence. This is in agreement with simulations of the spin dynamics of the system during WURST pulse excitation. The technique demonstrated here should allow more sensitive experiments to be measured away from the CT at higher operating temperatures, and be combined with any relevant pulse sequence.

Synergy of Magnetic Anisotropy and Ferromagnetic Interaction Triggering a Dimeric Cr(II) Zero-Field Single-Molecule Magnet

A novel CrII-dimeric complex, [CrIIN(SiiPr3)2(μ-Cl)(THF)]2 (1), has been successfully constructed using a bulky silyl-amide ligand. Single-crystal structure analysis reveals that complex 1 exhibits a binuclear motif, with a Cr2Cl2 rhombus core, where two equivalent tetra-coordinate CrII centers in the centrosymmetric unit display quasi-square planar geometry. The crystal structure has been well simulated and explored by density functional theory calculations. The axial zero-field splitting parameter (D < 0) with a small rhombic (E) value is unambiguously determined by systematic investigations of magnetic measurements, high-frequency electron paramagnetic resonance spectroscopy, and ab initio calculations. Remarkably, ac magnetic susceptibility data unveil that 1 features slow dynamic magnetic relaxation typical of single-molecule magnet behavior with Ueff = 22 K in the absence of a dc field. This increases up to 35 K under a corresponding static field. Moreover, magnetic studies and theoretical calculations point out that a non-negligible ferromagnetic coupling (FMC) exists in the dimeric Cr-Cr units of 1. The coexistence of magnetic anisotropy and FMC contributes to the first case of CrII-based single-molecule magnets (SMMs) under zero dc field.

Insights into the phototautomerism of free-base 5, 10, 15, 20-tetrakis(4-sulfonatophenyl) porphyrin.

Phototautomerism in the excited states of free-base 5, 10, 15, 20-tetrakis(4-sulfonatophenyl) porphyrin (H2TPPS4-) has been investigated combining, for the first time, advanced Electron Paramagnetic Resonance (EPR) with fluorescence and Raman spectroscopy. Triplet EPR spectroscopy, performed in protic and deuterated solvents and in the presence of photoselection, confirms the occurrence of phototautomerization and additionally suggests the formation of the cis tautomer as a minor component. The zero-field splitting parameters and triplet sublevel populations indicate that the process is slow in the triplet state. The results obtained by EPR combined with photoselection and fluorescence anisotropy have been interpreted within a model which accounts for a fast trans-trans tautomerization promoted by a spin-vibronic coupling mechanism for intersystem crossing, with an even distribution of the two trans tautomers at liquid nitrogen temperatures for H2TPPS4-.

Two Shared Icosahedral Metallacarboranes through Iron: A Joint Experimental and Theoretical Refinement of Mössbauer Spectrum in [Fe(1,2-C2B9H11)2]Cs.

Mössbauer and X-ray photoelectron spectroscopies (XPS) are complemented with high-level quantum-chemical computations in the study of the geometric and electronic structure of the paramagnetic salt of the metallacarborane sandwich complex [Fe(1,2-C2B9H11)2]Cs = FeSanCs. Experimental 57Fe isomer shifts and quadrupole splitting parameters are compared with the theoretical prediction, with good agreement. The appearance of two sets of Cs(3d) doublets in the XPS spectrum, separated by 2 eV, indicates that Cs has two different chemical environments due to ease of the Cs(+) cation moving around the sandwich complex with low-energy barriers, as confirmed by quantum-chemical computations. Several minimum-energy geometries of the FeSanCs structure with the corresponding energies and Mössbauer parameters are discussed, in particular the atomic charges and spin population and the surroundings of the Fe atom in the complex. The Mössbauer spectra were taken at different temperatures showing the presence of a low-spin Fe atom with S = 1/2 and thus confirming a paramagnetic FeIII species.

Zero-Field Splitting in Hexacoordinate Co(II) Complexes

A collection of 24 hexacoordinate Co(II) complexes was investigated by ab initio CASSCF + NEVPT2 + SOC calculations. In addition to the energies of spin–orbit multiplets (Kramers doublets, KD) their composition of the spins is also analyzed, along with the projection norm to the effective Hamiltonian. The latter served as the evaluation of the axial and rhombic zero-field splitting parameters and the g-tensor components. The fulfilment of spin-Hamiltonian (SH) formalism was assessed by critical indicators: the projection norm for the first Kramers doublet N(KD1) &gt; 0.7, the lowest g-tensor component g1 &gt; 1.9, the composition of KDs from the spin states |±1/2&gt; and |±3/2&gt; with the dominating percentage p &gt; 70%, and the first transition energy at the NEVPT2 level 4Δ1. Just the latter quantity causes a possible divergence of the second-order perturbation theory and a failure of the spin Hamiltonian. The data set was enriched by the structural axiality Dstr and rhombicity Estr, respectively, evaluated from the metal–ligand distances Co-O, Co-N and Co-Cl corrected to the mean values. The magnetic data (temperature dependence of the molar magnetic susceptibility, and the field dependence of the magnetization per formula unit) were fitted simultaneously, either to the Griffith–Figgis model working with 12 spin–orbit kets, or the SH-zero field splitting model that utilizes only four (fictitious) spin functions. The calculated data were analyzed using statistical methods such as Cluster Analysis and the Principal Component Analysis.