Institute of General and Inorganic Chemistry

The infrared spectral performance of the N x O y species observed on oxide surfaces [N2O, NO−, NO, (NO)2, N2O3, NO+, NO2 − (different nitro and nitrito anions), NO2, N2O4, N2O5, NO2, and NO3 − (bridged, bidentate, and monodentate nitrates)] is considered. The spectra of related compounds (N2, H-, and C-containing nitrogen oxo species, C─N species, NH x species) are also briefly discussed. Some guidelines for spectral identification of N x O y adspecies are proposed and the transformation of the nitrogen oxo species on catalyst surfaces are regarded.

The variety of functionalities and porous structures inherent to metal-organic frameworks (MOFs) together with the facile tunability of their properties makes these materials suitable for a wide range of existing and emerging applications. Many of these applications are based on processes involving interaction of MOFs with guest molecules. To optimize a certain process or successfully design a new one, a thorough knowledge is required about the physicochemical characteristics of materials and the mechanisms of their interaction with guest molecules. To obtain such important information, various complementary analytical techniques are applied, among which vibrational spectroscopy (IR and Raman) plays an important role and is indispensable in many cases. In this review, we critically examine the reported applications of IR and Raman spectroscopies as powerful tools for initial characterization of MOF materials and for studying processes of their interaction with various gases. Both the advantages and the limitations of the technique are considered, and the cases where IR or Raman spectroscopy is preferable are highlighted. Peculiarities of MOFs interaction with specific gases and some inconsistent band assignments are also emphasized. Summarizing the broad analytical possibilities of the IR and Raman spectroscopies, we conclude that it can be applied in combinations with other techniques to explicitly establish the structure, properties, and reactivity of MOFs.

A series of two-coordinate complexes of iron(II) were prepared and studied for single-molecule magnet behavior. Five of the compounds, Fe[N(SiMe3)(Dipp)]2 (1), Fe[C(SiMe3)3]2 (2), Fe[N(H)Ar′]2 (3), Fe[N(H)Ar*]2 (4), and Fe(OAr′)2 (5) feature a linear geometry at the FeII center, while the sixth compound, Fe[N(H)Ar#]2 (6), is bent with an N–Fe–N angle of 140.9(2)° (Dipp = C6H3-2,6-Pri2; Ar′ = C6H3-2,6-(C6H3-2,6-Pri2)2; Ar* = C6H3-2,6-(C6H2-2,4,6-Pri2)2; Ar# = C6H3-2,6-(C6H2-2,4,6-Me3)2). Ac magnetic susceptibility data for all compounds revealed slow magnetic relaxation under an applied dc field, with the magnetic relaxation times following a general trend of 1 > 2 > 3 > 4 > 5 ≫ 6. Arrhenius plots created for the linear complexes were fit by employing a sum of tunneling, direct, Raman, and Orbach relaxation processes, resulting in spin reversal barriers of Ueff = 181, 146, 109, 104, and 43 cm−1 for 1–5, respectively. CASSCF/NEVPT2 calculations on the crystal structures were performed to explore the influence of deviations from rigorous D∞h geometry on the d-orbital splittings and the electronic state energies. Asymmetry in the ligand fields quenches the orbital angular momentum of 1–6, but ultimately spin–orbit coupling is strong enough to compensate and regenerate the orbital moment. The lack of simple Arrhenius behavior in 1–5 can be attributed to a combination of the asymmetric ligand field and the influence of vibronic coupling, with the latter possibility being suggested by thermal ellipsoid models to the diffraction data.

Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials.

Using a combination of state-of-the-art computational modeling and Fourier transform infrared (FTIR) spectroscopy study of the surface species formed during interaction of CO2 or CO with activated (stoichiometric), reduced, and hydroxylated ceria, CeO2, we assigned various experimentally observed vibrational modes to individual types of surface species. We considered carbonates CO32–, formates HCO2–, and hydrogen carbonates CO2(OH)− bound in various ways to the surface of a ceria nanoparticle. Since the structure of the surface carbonate species is particularly versatile, we introduced a notation of different types of such species and computationally determined the regions where the characteristic vibrational frequencies of each type of species can be found. The complementary FTIR measurements of the surface species produced under different conditions revealed the actual experimental vibrational peaks and allowed estimation of the accuracy of the computational method to reproduce the frequencies of different vibrational modes. Thus, combining computed and experimental data we suggest a sound, partly new assignment of the vibrational bands in the complex IR spectra of surface (hydrogen)carbonate and formate species on ceria. The proposed reassignment of the vibrational peaks enables reliable detection of the surface species on ceria surface using vibrational spectroscopy. This is critical for the meaningful analysis of the reactivity of these species and the clarification of the mechanisms of the rich variety of surface processes on ceria.

Cobalt unfettered by its ligand field Applied magnetic fields induce a field in any compound with unpaired electrons. However, for the induced field to persist once the applied field is gone, the electrons must be configured to manifest orbital angular momentum. Generally, the influence of ligands severely restricts that property in transition metal complexes. Bunting et al. now show that a cobalt ion is just barely affected by two linearly coordinated carbon ligands and, as such, exhibits maximal orbital angular momentum. Although its magnetic properties mainly pertain at very low temperature, its structure offers a more general design principle. Science , this issue p. eaat7319

Proton conductors, catalysts, and solar energy storage materials are some of the potential uses of various crystalline acid salts of tetravalent metals. Results obtained on a large number of metal( IV ) phosphates and phosphonates are reviewed, the α‐ and β‐structured layered metal( IV ) phosphates and the organic derivatives of zirconium phosphates being emphasized. Methods of preparation and the structures determined—especially layered and pillared—are described.

The high charge-state dopant Zr⁴⁺ improves the structural stability and electrochemical behavior of the lithiated transition metal oxide LiNi_0.6Co_0.2Mn_0.2O₂.

The electronic structure and magnetic anisotropy of six complexes of high-spin FeII with linear FeX2 (X = C, N, O) cores, Fe[N(SiMe3)(Dipp)]2 (1), Fe[C(SiMe3)3]2 (2), Fe[N(H)Ar′]2 (3), Fe[N(H)Ar*]2 (4), Fe[O(Ar′)]2 (5), and Fe[N(t-Bu)2]2 (7) [Dipp = C6H3-2,6-Pri2; Ar′ = C6H3-2,6-(C6H3-2,6-Pri2)2; Ar* = C6H3-2,6-(C6H2-2,4,6-Pri2)2; Ar# = C6H3-2,6-(C6H2-2,4,6-Me3)2], and one bent (FeN2) complex, Fe[N(H)Ar#]2 (6), have been studied theoretically using complete active space self-consistent field (CASSCF) wavefunctions in conjunction with N-Electron Valence Perturbation Theory (NEVPT2) and quasidegenerate perturbation theory (QDPT) for the treatment of magnetic field and spin-dependent relativistic effects. Mössbauer studies on compound 2 indicate an internal magnetic field of unprecedented magnitude (151.7 T) at the FeII nucleus. This has been interpreted as arising from first order angular momentum of the 5Δ ground state of FeII center (J. Am. Chem. Soc. 2004, 126, 10206). Using geometries from X-ray structural data, ligand field parameters for the Fe-ligand bonds were extracted using a 1 : 1 mapping of the angular overlap model onto multireference wavefunctions. The results demonstrate that the metal–ligand bonding in these complexes is characterized by: (i) strong 3dz2–4s mixing (in all complexes), (ii) π-bonding anisotropy involving the strong π-donor amide ligands (in 1, 3–4, 6, and 7) and (iii) orbital mixings of the σ–π type for Fe–O bonds (misdirected valence in 5). The interplay of all three effects leads to an appreciable symmetry lowering and splitting of the 5Δ (3dxy, 3dx2−y2) ground state. The strengths of the effects increase in the order 1 < 5 < 7 ∼ 6. However, the differential bonding effects are largely overruled by first-order spin–orbit coupling, which leads to a nearly non-reduced orbital contribution of L = 1 to yield a net magnetic moment of about 6 μB. This unique spin–orbital driven magnetism is significantly modulated by geometric distortion effects: static distortions for the bent complex 6 and dynamic vibronic coupling effects of the Renner–Teller type of increasing strength for the series 1–5.Ab initio calculations based on geometries from X-ray data for 1 and 2 reproduce the magnetic data exceptionally well. Magnetic sublevels and wavefunctions were calculated employing a dynamic Renner–Teller vibronic coupling model with vibronic coupling parameters adjusted from the ab initio results on a small Fe(CH3)2 truncated model complex. The model reproduces the observed reduction of the orbital moments and quantitatively reproduces the magnetic susceptibility data of 3–5 after introduction of the vibronic coupling strength (f) as a single adjustable parameter. Its value varies in a narrow range (f = 0.142 ± 0.015) across the series. The results indicate that the systems are near the borderline of the transition from a static to a dynamic Renner–Teller effect. Renner–Teller vibronic activity is used to explain the large reduction of the spin-reversal barrier Ueff along the series from 1 to 5. Based upon the theoretical analysis, guidelines for generating new single-molecule magnets with enhanced magnetic anisotropies and longer relaxation times are formulated.

Adsorption of NO and its co-adsorption with oxygen on TiO2 (Degussa P-25) were studied by FTIR spectroscopy. It was found that NO adsorption results in its disproportionation to NO− (1170 cm−1), N2O22− (1335 cm−1) and nitrates (1650–1550 and 1240–1220 cm−1). The nitrate bands develop with time and coordinated NO (ca. 1900 cm−1) is formed. Addition of oxygen to NO results in a strong increase in concentration of the nitrates and formation of NO+ (2206 cm−1). In addition, species assigned to nitrocomplexes (1520 and 1284 cm−1) are found. The stability and reactivity of the different surface compounds as well as their interconversion are studied and discussed.

Manganese substituted sodium cobaltate, Na(2/3)Co(2/3)Mn(1/3)O(2), with a layered hexagonal structure (P2-type) was obtained by a co-precipitation method followed by a heat treatment at 950 °C. Powder X-ray diffraction analysis revealed that the phase is pure in the absence of long-range ordering of Co and Mn ions in the slab or Na(+) and vacancy in the interslab space. The oxidation states of the transition metal ions were studied by magnetic susceptibility measurements, electron paramagnetic resonance (ESR) and (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The charge compensation is achieved by the stabilization of low-spin Co(3+) and Mn(4+) ions. The capability of Na(2/3)Co(2/3)Mn(1/3)O(2) to intercalate and deintercalate Na(+) reversibly was tested in electrochemical sodium cells. It appears that the P2 structure is maintained during cycling, the cell parameter evolution versus the sodium amount is given. From the features of the cycling curve the formation of an ordered phase for the Na(0.5)Co(2/3)Mn(1/3)O(2) composition is expected.

The exact equations for the unary and binary distribution functions derived in [1] contain infinite functionals M (i), i=1, 2, whose calculation encounters considerable difficulties. These equations cannot therefore find practical application. A method has been suggested for an approximation of these functionals. Even in the first approximation, this method leads to an equation which enables the pressure in a system of high-density hard spheres to be calculated with an accuracy ten times higher than that of the Percus-Yevick equation and 25 times higher than the accuracy of the HNC equation.

, exceeding the capacity of graphite. These results open the door for a new class of high capacity anode materials (based on sulfide chemistry) for potassium-ion batteries.

Heavier group 14 multiple bonds have intrigued chemists since more than a century. The synthesis of stable compounds with double and triple bonds with silicon, germanium, tin and lead had considerable impact on modern ideas of chemical bonding. These developments were made possible by the use of bulky substituents that provide kinetic and thermodynamic protection. Since about a decade the compatibility of heavier multiple bonds with various functional groups has moved into focus. This review covers multiply bonded group 14 species with at least one additional reactive site. The vinylic functionalities of groups 1 and 17, resulting in nucleophilic and electrophilic disila vinyl groups, respectively, are the most prevalent and well-studied. They have been employed repeatedly for the transfer of heavier multiple bonds to yield low-valent group 14 compounds with novel structural motifs. Vinylic functionalities of groups 2 to 16 and a few σ-bonded transition metal complexes are experimentally known, but their reactivity has been studied to a lesser extent. Donor-coordinated multiple bonds are a relatively new field of research, but the large degree of unsaturation as isomers of alkynes (as well as residual functionality in some cases) offers considerable possibility for further manipulation, e.g. for the incorporation into more extended systems. Heavier allyl halides constitute the major part of heavier multiple bonds with a functional group in allylic position and some examples of successful transformations are given. At present, remote functionalities are basically limited to para-phenylene functionalised disilenes. The reported use of the latter for further derivatisation might encourage investigations in this direction. In summary, the study of peripherally functionalised multiple bonds with heavier group 14 elements is already well beyond its infancy and may be an instrumental factor in awakening the potential of group 14 chemistry for applications in polymers and other materials.

A theoretical, computational, and conceptual framework for the interpretation and prediction of the magnetic anisotropy of transition metal complexes with orbitally degenerate or orbitally nearly degenerate ground states is explored. The treatment is based on complete active space self-consistent field (CASSCF) wave functions in conjunction with N-electron valence perturbation theory (NEVPT2) and quasidegenerate perturbation theory (QDPT) for treatment of magnetic field- and spin-dependent relativistic effects. The methodology is applied to a series of Fe(II) complexes in ligand fields of almost trigonal pyramidal symmetry as provided by several variants of the tris-pyrrolylmethyl amine ligand (tpa). These systems have recently attracted much attention as mononuclear single-molecule magnet (SMM) complexes. This study aims to establish how the ligand field can be fine tuned in order to maximize the magnetic anisotropy barrier. In trigonal ligand fields high-spin Fe(II) complexes adopt an orbitally degenerate (5)E ground state with strong in-state spin-orbit coupling (SOC). We study the competing effects of SOC and the (5)E⊗ε multimode Jahn-Teller effect as a function of the peripheral substituents on the tpa ligand. These subtle distortions were found to have a significant effect on the magnetic anisotropy. Using a rigorous treatment of all spin multiplets arising from the triplet and quintet states in the d(6) configuration the parameters of the effective spin-Hamiltonian (SH) approach were predicted from first principles. Being based on a nonperturbative approach we investigate under which conditions the SH approach is valid and what terms need to be retained. It is demonstrated that already tiny geometric distortions observed in the crystal structures of four structurally and magnetically well-documented systems, reported recently, i.e., [Fe(tpa(R))](-) (R = tert-butyl, Tbu (1), mesityl, Mes (2), phenyl, Ph (3), and 2,6-difluorophenyl, Dfp (4), are enough to lead to five lowest and thermally accessible spin sublevels described sufficiently well by S = 2 SH provided that it is extended with one fourth order anisotropy term. Using this most elementary parametrization that is consistent with the actual physics, the reported magnetization data for the target systems were reinterpreted and found to be in good agreement with the ab initio results. The multiplet energies from the ab initio calculations have been fitted with remarkable consistency using a ligand field (angular overlap) model (ab initio ligand field, AILFT). This allows for determination of bonding parameters and quantitatively demonstrates the correlation between increasingly negative D values and changes in the σ-bond strength induced by the peripheral ligands. In fact, the sigma-bonding capacity (and hence the Lewis basicity) of the ligand decreases along the series 1 > 2 > 3 > 4.

The paper addresses possible ambiguities in the determination of the state of platinum species by the stretching frequency of a CO probe, which is a common technique for characterization of platinum-containing catalytic systems. We present a comprehensive comparison of the available experimental data with our theoretical modeling (density functional) results of pertinent systems - platinum surfaces, nanoparticles and clusters as well as reduced or oxidized platinum moieties on a ceria support. Our results for CO adsorbed on-top on metallic Pt(0), with C-O vibrational frequencies in the region 2018-2077 cm(-1), suggest that a decrease of the coordination number of the platinum atom, to which CO is bound, by one lowers the CO frequency by about 7 cm(-1). This trend corroborates the Kappers-van der Maas correlation derived from the analysis of the experimental stretching frequency of CO adsorbed on platinum-containing samples on different supports. We also analyzed the effect of the charge of platinum species on the CO frequency. Based on the calculated vibrational frequencies of CO in various model systems, we concluded that the actual state of the platinum species may be mistaken based only on the measured value of the C-O vibrational frequency due to overlapping regions of frequencies corresponding to different types of species. In order to identify the actual state of platinum species one has to combine this powerful technique with other approaches.

The mainline feature in metal Kβ X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of Kβ mainline XES. Ligand field expressions are derived that describe the behavior of Kβ mainlines for first row transition metals with any d(n) count, allowing for a detailed analysis of the factors governing mainline shape. Further, due to limitations associated with existing computational approaches, we have developed a new methodology for calculating Kβ mainlines using restricted active space configuration interaction (RAS-CI) calculations. This approach eliminates the need for empirical parameters and provides a powerful tool for investigating the effects that chemical environment exerts on the mainline spectra. On the basis of a detailed analysis of the intermediate and final states involved in these transitions, we confirm the known sensitivity of Kβ mainlines to metal spin state via the 3p-3d exchange coupling. Further, a quantitative relationship between the splitting of the Kβ mainline features and the metal-ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from Kβ mainline spectroscopy.

Low-temperature CO adsorption on TiO2 (anatase) has been investigated by FTIR spectroscopy on (i) a pure sample, (ii) a sample on which the sites for CO adsorption at room temperature are blocked by ammonia, and (iii) anatase whose surface is covered by ammonia. Adsorption of small amounts of CO at 100 K on anatase leads to the appearance of two bands at 2210 and 2192 cm-1 due to CO adsorbed on two kinds (α and β‘, respectively) of Ti4+ sites (the same species are also observed when adsorbing CO at room temperature). The increase of the introduced CO amount involves sites (β‘‘-sites) that are inert at room temperature. The CO molecules adsorbed on β‘‘-sites interact with CO molecules preadsorbed on β‘ sites, as a result of which the two adsorption forms produce a common absorption band whose maximum is shifted to 2179 cm-1 at higher coverage. With increasing amount of adsorbed CO, one more kind (γ) of Ti4+ site with very weak acidity is detected, the corresponding absorption band being at 2165 cm-1. Under CO equilibrium pressure two additional reversible adsorption forms appear: CO H-bonded to surface hydroxyl groups (ν(CO) at 2155 cm-1) and physically adsorbed CO (band at 2138 cm-1). Simultaneously with the appearance and increase in intensity of the band at 2155 cm-1, a broadening and shift by about −115 cm-1 of the bands for the surface hydroxyl groups occur. Adsorption of a 13CO shows that the shifts of the bands at 2210 and 2192 cm-1 are mainly of a static type (−4 and −17 cm-1, respectively), the dynamic components being only +4 cm-1 for the β-carbonyls and not measurable for the α-carbonyls. CO adsorption on reduced anatase indicates the formation of the same types of carbonyls. However, in this case, part of the introduced CO probably dissociates and oxidizes the Ti3+ ions into Ti4+. Low-temperature CO adsorption on anatase on which the sites for CO adsorption at room temperature (the α and β‘ sites) are preliminary blocked by ammonia leads to the formation of carbonyls on β‘‘ and γ sites (ν(CO) at 2177 and 2156 cm-1, respectively), as well as of CO adsorbed on OH groups and physically adsorbed CO. In this case the shift of the OH stretching modes is still −115 cm-1. Low-temperature CO adsorption on anatase fully precovered with ammonia shows the appearance of weakly bound forms only: a part of the carbonyls on γ-sites (ν(CO) shifted to 2151 cm-1), CO adsorbed on hydroxyl groups, and physically adsorbed CO. However, in this case the shift of the ν(OH) stretching modes is only −65 cm-1. The nature of the different kinds of active sites for adsorption of ammonia and CO on anatase is discussed.

At room temperature CO is adsorbed strongly on Cu+ sites (band at 2131 cm−1) whereas NO is preferably adsorbed on Cu2+ sites (band at 1882 cm−1). Coadsorption of CO and NO allows simultaneous and selective detection of both kinds of cations. This observation is used to follow the changes on the sample surface occurring in the presence of oxygen. Addition of small amounts of O2 to the CO–NO–Cu/SiO2 system first leads to the oxidation of the Cu+ sites to Cu2+. This process is followed by formation of surface nitrates which block the Cu2+ sites for NO adsorption. Adsorption of CO at 85 K allows detection of Cu2+ cations (ca. 2200 cm−1) in addition to the Cu+, CO is replaced by NO from these sites. Cu0 sites form carbonyls which, when copper is highly dispersed, can absorb at the same frequency at which Cu+–CO carbonyls are detected. In this case both kinds of species could be distinguished by their stability: the Cu0–CO species are easily destroyed during evacuation.

Abstract Phthalic anhydride is one of the most important products of modem large-scale organic synthesis, and it has a wide application in various branches of chemical industry. It is mostly used (60% of the world production) for preparation plasticizers for PVC. The rapid development of the industrial production of polymeric materials during the last two decades increased the need of phthalic anhydride, which resulted in an increase of its production [1, 2].