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The synthesis and thermal degradation of MAl 4 (OH) 12 SO 4 ·3H 2 O layered double hydroxides with M = Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ("MAl 4 -LDH") were investigated by inductively coupled plasma-optical emission spectroscopy, thermogravimetric analysis, powder X-ray diffraction, Rietveld refinement, scanning electron microscopy, scanning tunnel electron microscopy, energy-dispersive X-ray spectroscopy, and solid-state 1 H and 27 Al NMR spectroscopy. Following extensive synthesis optimization, phase pure CoAl 4 - and NiAl 4 -LDH were obtained, whereas 10-12% unreacted bayerite (Al(OH) 3 ) remained for the CuAl 4 -LDH. The optimum synthesis conditions are hydrothermal treatment at 120 °C for 14 days (NiAl 4 -LDH only 9 days) with MSO 4 (aq) concentrations of 1.4-2.8, 0.7-0.8, and 0.08 M for the CoAl 4 -, NiAl 4 -, and CuAl 4 -LDH, respectively. A pH ≈ 2 for the metal sulfate solutions is required to prevent the formation of byproducts, which were Ni(OH) 2 and Cu 3 (SO 4 )(OH) 4 for NiAl 4 - and CuAl 4 -LDH, respectively. The thermal degradation of the three MAl 4 -LDH and ZnAl 4 -LDH in a nitrogen atmosphere proceeds in three steps: (i) dehydration and dehydroxylation between 200 and 600 °C, (ii) loss of sulfate between 600 and 900 °C, and (iii) formation of the end products at 900-1200 °C. For CoAl 4 -LDH (ZnAl 4 -LDH), these are α-Al 2 O 3 and CoAl 2 O 4 (ZnAl 2 O 4 ) spinel. For NiAl 4 -LDH, a spinel-like NiAl 4 O 7 phase forms, whereas CuAl 4 -LDH degrades by a redox reaction yielding a diamagnetic CuAlO 2 (delafossite structure) and α-Al 2 O 3 .

In this paper, we experimentally study and model the electron donating character of an axial diamagnetic Pd 2+ ion in four metalloligated lanthanide complexes of formula [PPh 4 ][Ln{Pd(SAc) 4 } 2 ] (SAc - = thioacetate, Ln = Tb, Dy, Ho, and Er). A global model encompassing inelastic neutron scattering, torque magnetometry, and dc magnetometry allows to precisely determine the energy level structure of the complexes. Solid state nuclear magnetic resonance reveals a less donating character of Pd 2+ compared to the previously reported isostructural Pt 2+ -based complexes. Consequently, all complexes invariably show a lower crystal field strength compared to their Pt 2+ -analogues. The dynamic properties show an enhanced single molecule magnet behavior due to the suppression of quantum tunneling, in agreement with our model.

The phase purity of a series of ZnAl 4 (OH) 12 SO 4 · nH 2 O layered double hydroxides (ZnAl 4 -LDH) obtained from a reaction of bayerite (Al(OH) 3 ) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e., crystalline impurities, Al impurities, and bulk Zn:Al ratio, were assessed by powder X-ray diffraction (PXRD), 27 Al MAS NMR, and elemental analysis. Structural characterization of a stoichiometric ZnAl 4 -LDH (120 °C, 9 days, and 2.8 M Zn(II)) showed a well-defined structure of the metal ion layer as evidenced by a single, well-defined Zn environment: i.e., no Zn substitution on the Al sites according to Zn k-edge EXAFS and PXRD. Furthermore, nearly all of the 12 different 1 H atoms in the -OH groups and 4 27 Al resonances could be assigned using 1 H, 27 Al NMR correlation experiments recorded with ultrafast MAS. The interlayer water content is variable on the basis of thermogravimetric analysis and changes in the 1 H MAS NMR spectra with temperature. A composition of ZnAl 4 (OH) 12 (SO 4 )·2.6H 2 O was obtained from a combination of these techniques and confirmed that ZnAl 4 -LDH is isostructural with the mineral nickelalumite (NiAl 4 (OH) 12 SO 4 ·3H 2 O).

Bayerite was treated under hydrothermal conditions (120, 130, 140, and 150 °C) to prepare a series of layered double hydroxides (LDHs) with an ideal composition of ZnAl4(OH)12(SO4)0.5·nH2O (ZnAl4-LDHs). These products were investigated by both bulk techniques (powder X-ray diffraction (PXRD), transmission electron microscopy, and elemental analysis) and atomic-level techniques ((1)H and (27)Al solid-state NMR, IR, and Raman spectroscopy) to gain a detailed insight into the structure of ZnAl4-LDHs and sample composition. Four structural models (one stoichiometric and three different defect models) were investigated by Rietveld refinement of the PXRD data. These were assessed using the information obtained from other characterization techniques, which favored the ideal (nondefect) structural model for ZnAl4-LDH, as, for example, (27)Al magic-angle spinning NMR showed that excess Al was present as amorphous bayerite (Al(OH)3) and pseudoboehmite (AlOOH). Moreover, no evidence of cation mixing, that is, partial substitution of Zn(II) onto any of four Al sites, was observed. Altogether this study highlights the challenges involved to synthesize pure ZnAl4-LDHs and the necessity to use complementary techniques such as PXRD, elemental analysis, and solid-state NMR for the characterization of the local and extended structure of ZnAl4-LDHs.

Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)2] and trans-[Ni(acac)2(X)2]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe]1/2, n = 0 or 1, dppe = 1,2-bis(diphenylphosphino)ethane, as well as cis-[Ni(F6-acac)2(D2O)2], F6-acac = hexafluoroacetylonato, have been characterized by solid state (13)C MAS NMR spectroscopy. (2)H MAS NMR was used to probe the local hydrogen bonding network in [Ni(acac)2(D2O)2]D2O and cis-[Ni(F6-acac)2(D2O)2]. The complexes serve to benchmark the paramagnetic shift, which can be associated with the resonances of atoms of the coordinated ligands. The methine (CH) and methyl (CH3) have characteristic combinations of the isotropic shift (δ) and anisotropy parameters (d, η). The size of the anisotropy (d), which is the sum of the chemical shift anisotropy (CSA) and the paramagnetic electron-nuclei dipolar coupling, is much more descriptive than the isotropic shift. Moreover, the CSA is found to constitute up to one-third of the total anisotropy and should be taken into consideration when (13)C anisotropies are used for structure determination of paramagnetic materials. The (13)C MAS NMR spectra of trans-[Ni(acac)2(PMe2Ph)2], trans-[Ni(acac)2(PMePh2)2], and the noncrystallographically characterized trans-[Ni(acac)2(dppe)]n were assigned using these correlations. The complexes with L = H2O, D2O, NH3, and MeOH can be prepared by a series of solid state desorption and sorption reactions. Crystal structures for trans-[Ni(acac)2(NH3)2] and trans-[Ni(acac)2(PMePh2)2] are reported.

A matched set of dinuclear cobalt complexes with II-II, II-III, and III-III oxidation states have been prepared and structurally characterized. In [(bpbp)Co2(O2P(OPh)2)2]n+ ( n = 1, 2, or 3; bpbp(-) = 2,6-bis(( N,N'-bis-(2-picolyl)amino)-methyl)-4-tertbutylphenolato), the nonbonded Co...Co separations are within the range 3.5906(17) to 3.7081(11) angstroms, and the metal ions are triply bridged by the phenolate oxygen atom of the heptadentate dinucleating ligand and by two diphenylphosphate groups. The overall structures and geometries of the complexes are very similar, with minor variations in metal-ligand bond distances consistent with oxidation state assignments. The CoIICoIII compound is a valence-trapped Robin-Day class II complex. Solid state 31P NMR spectra of the diamagnetic CoIIICoIII (3) and paramagnetic CoIICoIII (2) and CoIICoII (1) complexes show that 31P isotropic shifts broaden and move downfield by about 3000 ppm for each increment in oxidation state. Cyclic voltammetry corroborates the existence of the CoIICoII, CoIICoIII, and CoIIICoIII species in solution. The redox changes are not reversible in the applied scanning timescales, indicating that chemical changes are associated with oxidation and reduction of the cobalt centers. An investigation of the spectroscopic properties of this series has been carried out for its potential usefulness in analyses of the related spectroscopic properties of the dicobalt metallohydrolases. Principally, magnetic circular dichroism (MCD) has been used to determine the strength of the magnetic exchange coupling in the CoIICoII complex by analysis of the variable-temperature variable-field (VTVH) intensity behavior of the MCD signal. The series is ideal for the spectroscopic determination of magnetic coupling since it can occur only in the CoIICoII complex. The CoIICoIII complex contains a nearly isostructural CoII ion, but since CoIII is diamagnetic, the magnetic coupling is switched off, while the spectral features of the CoII ion remain. Analysis of the MCD data from the CoIICoIII complex has been undertaken in the theoretical context of a 4T1g ground-state of the CoII ion, initially in an octahedral ligand field that is split by both geometric distortion and zero-field splitting to form an isolated doublet ground state. The MCD data for the CoIICoII pair in the [(bpbp)Co2(O2P(OPh)2)2]+ complex were fitted to a model based on weak antiferromagnetic coupling with J = -1.6 cm (-1). The interpretation is confirmed by solid state magnetic susceptibility measurements.

Polycrystalline samples of AlVO(4) have been prepared by two methods of synthesis and characterized by (27)Al and (51)V MAS NMR spectroscopy at 14.1 T. The MAS NMR spectra clearly reveal that essentially pure samples with minor impurities of V(2)O(5) and alumina have been obtained. From these samples, (27)Al quadrupole coupling parameters and isotropic chemical shifts as well as the magnitudes and relative orientations of the (51)V quadrupole coupling and chemical shift tensors have been determined with high precision for AlVO(4). These data have been obtained from a combined analysis of multiple-quantum (MQ) MAS NMR spectra and MAS NMR spectra of the central and satellite transitions. The (27)Al and (51)V NMR data show that the asymmetric unit for AlVO(4) contains three isolated VO(4) tetrahedra, one pentacoordinated Al site, and two AlO(6) octahedra. This is in agreement with the supposition that AlVO(4) is isostructural with FeVO(4) and with a recent structure refinement for AlVO(4) based on powder X-ray diffraction (XRD) data. The favorable agreement between the refined crystal structure from powder XRD and the NMR parameters is apparent from a convincing correlation between experimental (51)V quadrupole tensor elements and calculated (51)V electric field gradient tensor elements obtained by the point-monopole approach. An assignment of the (27)Al NMR data is obtained from similar calculations of the (27)Al electric field gradients and by estimation of the distortion of the AlO(6) octahedra.

51V quadrupole coupling and chemical shielding tensors have been determined from 51V magic-angle spinning (MAS) NMR spectra at a magnetic field of 14.1 T for nine divalent metal metavanadates: Mg(VO3)2, Ca(VO3)2, Ca(VO3)(2).4H2O, alpha-Sr(VO3)2, Zn(VO3)2, alpha- and beta-Cd(VO3)2. The manifold of spinning sidebands (ssbs) from the central and satellite transitions, observed in the 15V MAS NMR spectra, have been analyzed using least-squares fitting and numerical error analysis. This has led to a precise determination of the eight NMR parameters characterizing the magnitudes and relative orientations of the quadrupole coupling and chemical shielding tensors. The optimized data show strong similarities between the NMR parameters for the isostructural groups of divalent metal metavanadates. This demonstrates that different types of metavanadates can easily be distinguished by their anisotropic NMR parameters. The brannerite type of divalent metal metavanadates exhibits very strong 51V quadrupole couplings (i.e., CQ = 6.46-7.50 MHz), which reflect the highly distorted octahedral environments for the V5+ ion in these phases. Linear correlations between the principal tensor elements for the 51V quadrupole coupling tensors and electric field gradient tensor elements, estimated from point-monopole calculations, are reported for the divalent metal metavanadates. These correlations are used in the assignment of the NMR parameters for the different crystallographic 51V sites of Ca(VO3)(2).4H2O, Pb(VO3)2, and Ba(VO3)2. For alpha-Sr(VO3)2, with an unknown crystal structure, the 51V NMR data strongly suggest that this metavanadate is isostructural with Ba(VO3)2, for which the crystal structure has been reported. Finally, the chemical shielding parameters for orthovanadates and mono- and divalent metal metavanadates are compared.