Chemical shifts present crucial information about an NMR spectrum. They show the influence of the chemical environment on the nuclei being probed. Relativistic effects caused by the presence of an ...atom of a heavy element in a compound can appreciably, even drastically, alter the NMR shifts of the nearby nuclei. A fundamental understanding of such relativistic effects on NMR shifts is important in many branches of chemical and physical science. This review provides a comprehensive overview of the tools, concepts, and periodic trends pertaining to the shielding effects by a neighboring heavy atom in diamagnetic systems, with particular emphasis on the “spin-orbit heavy-atom effect on the light-atom” NMR shift (SO-HALA effect). The analyses and tools described in this review provide guidelines to help NMR spectroscopists and computational chemists estimate the ranges of the NMR shifts for an unknown compound, identify intermediates in catalytic and other processes, analyze conformational aspects and intermolecular interactions, and predict trends in series of compounds throughout the Periodic Table. The present review provides a current snapshot of this important subfield of NMR spectroscopy and a basis and framework for including future findings in the field.
This paper describes the application of eye tracking technology in the automotive industry in the context of vehicle assessment in customer clinics. The paper presents the mentioned technology, the ...applied experimental methodology and selected results. In particular, the hypotheses that were expressed during the research of the topic and during the preparation of the experiment are answered. In this way, the innovative technology of eye tracking can be used to reflect the "voice of the customer" in the vehicle design.
Theoretical interpretation of hyperfine interactions was pioneered in the 1950s–1960s by the seminal works of McConnell, Karplus, and others for organic radicals and by Watson and Freeman for ...transition-metal (TM) complexes. In this work, we investigate a series of octahedral Ru(III) complexes with aromatic ligands to understand the mechanism of transmission of the spin density from the d-orbital of the metal to the s-orbitals of the ligand atoms. Spin densities and spin populations underlying ligand hyperfine couplings are analyzed in terms of π-conjugative or σ-hyperconjugative delocalization vs spin polarization based on symmetry considerations and restricted open-shell vs unrestricted wave function analysis. The transmission of spin density is shown to be most efficient in the case of symmetry-allowed π-conjugative delocalization, but when the π-conjugation is partially or fully symmetry-forbidden, it can be surpassed by σ-hyperconjugative delocalization. Despite a lower spin population of the ligand in σ-hyperconjugative transmission, the hyperfine couplings can be larger because of the direct involvement of the ligand s-orbitals in this delocalization pathway. We demonstrate a quantitative correlation between the hyperfine couplings of aromatic ligand atoms and the characteristics of the metal–ligand bond modulated by the trans substituent, a hyperfine trans effect.
Despite the extensive knowledge about the effects of chronic stress on cognition, the underlying mechanisms remain unclear. We conducted a cross-sectional moderation analysis on a population-based ...sample of 596 adults to examine the age- and sex-specific role of emotion regulation (ER) in the relationship between chronic stress and cognitive performance using validated self-report questionnaires. While women showed no direct or moderated relationship between stress and cognition, men displayed a distinct age-related pattern where stress was negatively associated with poorer cognitive performance at older ages, and the onset of this relationship was detected earlier in men with ER problems. These results showed that suppression of emotions and lack of executive control of ER amplify the negative consequences of chronic stress and suggest that there are sex-specific differences in the decline of ability to cope with long-term exposure to stressors.
Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this ...study we focus on paramagnetic NAMI analogs of a general structure 4-R-pyH+ trans-RuIIICl4(DMSO)(4-R-py)−, where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the 1H and 13C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (δorb, temperature-independent) and paramagnetic (δpara, temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the 13C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the 13C isotropic hyperfine coupling constants, A iso(13C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin–orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on δpara, particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account.
Spherically symmetric equilibrium configurations of perfect fluid obeying a polytropic equation of state are studied in spacetimes with a repulsive cosmological constant. The configurations are ...specified in terms of three parameters-the polytropic index n, the ratio of central pressure and central energy density of matter σ, and the ratio of energy density of vacuum and central density of matter λ. The static equilibrium configurations are determined by two coupled first-order nonlinear differential equations that are solved by numerical methods with the exception of polytropes with n=0 corresponding to the configurations with a uniform distribution of energy density, when the solution is given in terms of elementary functions. The geometry of the polytropes is conveniently represented by embedding diagrams of both the ordinary space geometry and the optical reference geometry reflecting some dynamical properties of the geodesic motion. The polytropes are represented by radial profiles of energy density, pressure, mass, and metric coefficients. For all tested values of n>0, the static equilibrium configurations with fixed parameters n, σ, are allowed only up to a critical value of the cosmological parameter λc=λc(n,σ). In the case of n>3, the critical value λc tends to zero for special values of σ. The gravitational potential energy and the binding energy of the polytropes are determined and studied by numerical methods. We discuss in detail the polytropes with an extension comparable to those of the dark matter halos related to galaxies, i.e., with extension ℓ>100 kpc and mass M>1012 M⊙. For such largely extended polytropes, the cosmological parameter relating the vacuum energy to the central density has to be larger than λ=ρvac/ρc∼10−9. We demonstrate that the extension of the static general relativistic polytropic configurations cannot exceed the so-called static radius related to their external spacetime, supporting the idea that the static radius represents a natural limit on the extension of gravitationally bound configurations in an expanding universe dominated by the vacuum energy.
Relativistic effects significantly affect various spectroscopic properties of compounds containing heavy elements. Particularly in Nuclear Magnetic Resonance (NMR) spectroscopy, the heavy atoms ...strongly influence the NMR shielding constants of neighboring light atoms. In this account we analyze paramagnetic contributions to NMR shielding constants and their modulation by relativistic spin–orbit effects in a series of transition-metal complexes of Pt(II), Au(I), Au(III), and Hg(II). We show how the paramagnetic NMR shielding and spin–orbit effects relate to the character of the metal–ligand (M–L) bond. A correlation between the (back)-donation character of the M–L bond in d10 Au(I) complexes and the propagation of the spin–orbit (SO) effects from M to L through the M–L bond influencing the ligand NMR shielding via the Fermi-contact mechanism is found and rationalized by using third-order perturbation theory. The SO effects on the ligand NMR shielding are demonstrated to be driven by both the electronic structure of M and the nature of the trans ligand, sharing the σ-bonding metal orbital with the NMR spectator atom L. The deshielding paramagnetic contribution is linked to the σ-type M–L bonding orbitals, which are notably affected by the trans ligand. The SO deshielding role of σ-type orbitals is enhanced in d10 Hg(II) complexes with the Hg 6p atomic orbital involved in the M–L bonding. In contrast, in d8 Pt(II) complexes, occupied π-type orbitals play a dominant role in the SO-altered magnetic couplings due to the accessibility of vacant antibonding σ-type MOs in formally open 5d-shell (d8). This results in a significant SO shielding at the light atom. The energy- and composition-modulation of σ- vs π-type orbitals by spin–orbit coupling is rationalized and supported by visualizing the SO-induced changes in the electron density around the metal and light atoms (spin–orbit electron deformation density, SO-EDD).
Understanding how the electronic g-tensor is linked to the electronic structure is desirable for the correct interpretation of electron paramagnetic resonance spectra. For heavy-element compounds ...with large spin–orbit (SO) effects, this is still not completely clear. We report our investigation of quadratic SO contributions to the g-shift in heavy transition metal complexes. We implemented third-order perturbation theory in order to analyze the contributions arising from frontier molecular spin orbitals (MSOs). We show that the dominant quadratic SO termspin-Zeeman (SO2/SZ)generally makes a negative contribution to the g-shift, irrespective of the particular electronic configuration or molecular symmetry. We further analyze how the SO2/SZ contribution adds to or subtracts from the linear orbital-Zeeman (SO/OZ) contribution to the individual principal components of the g-tensor. Our study suggests that the SO2/SZ mechanism decreases the anisotropy of the g-tensor in early transition metal complexes and increases it in late transition metal complexes. Finally, we apply MSO analysis to the investigation of g-tensor trends in a set of closely related Ir and Rh pincer complexes and evaluate the influence of different chemical factors (the nuclear charge of the central atom and the terminal ligand) on the magnitudes of the g-shifts. We expect our conclusions to aid the understanding of spectra in magnetic resonance investigations of heavy transition metal compounds.
Nuclear magnetic resonance (NMR) spectroscopy of paramagnetic molecules provides detailed information about their molecular and electron-spin structure. The paramagnetic NMR spectrum is a very rich ...source of information about the hyperfine interaction between the atomic nuclei and the unpaired electron density. The Fermi-contact contribution to ligand hyperfine NMR shifts is particularly informative about the nature of the metal–ligand bonding and the structural arrangements of the ligands coordinated to the metal center. In this account, we provide a detailed experimental and theoretical NMR study of compounds of Cr(III) and Cu(II) coordinated with substituted acetylacetonate (acac) ligands in the solid state. For the first time, we report the experimental observation of extremely paramagnetically deshielded 13C NMR resonances for these compounds in the range of 900–1200 ppm. We demonstrate an excellent agreement between the experimental NMR shifts and those calculated using relativistic density-functional theory. Crystal packing is shown to significantly influence the NMR shifts in the solid state, as demonstrated by theoretical calculations of various supramolecular clusters. The resonances are assigned to individual atoms in octahedral Cr(acac)3 and square-planar Cu(acac)2 compounds and interpreted by different electron configurations and magnetizations at the central metal atoms resulting in different spin delocalizations and polarizations of the ligand atoms. Further, effects of substituents on the 13C NMR resonance of the ipso carbon atom reaching almost 700 ppm for Cr(acac)3 compounds are interpreted based on the analysis of Fermi-contact hyperfine contributions.
The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ...ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na+trans-RuIIICl4(DMSO)(L)− (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbitnuril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host–guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.
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