ABSTRACT
Invited for the cover of this issue is Cyril Aymonier and co-workers at University of Bordeaux and University of the Basque Country. The image depicts the different distributions of water molecules in xonotlite and tobermorite nanominerals synthesised in supercritical water. Read the full text of the article at 10.1002/chem.202100098.
Subject(s)
Water , Calcium Compounds , Humans , SilicatesABSTRACT
Calcium silicate hydrates are members of a large family of minerals with layered structures containing pendant CaOH and SiOH groups that interact with confined water molecules. To rationalize the impact of the local chemical environment on the dynamics of water, SiOH- and CaOH-rich model nanocrystals were synthesized by using the continuous supercritical hydrothermal method and then systematically studied by a combination of spectroscopic techniques. In our comprehensive analysis, the ultrafast relaxation dynamics of hanging hydroxy groups can be univocally assigned to CaOH or SiOH environments, and the local chemical environment largely affects the H-bond network of the solvation water. Interestingly, the ordered "ice-like" solvation water found in the SiOH-rich environments is converted to a disordered "liquid-like" distribution in the CaOH-rich environment. This refined picture of the dynamics of confined water and hydroxy groups in calcium silicate hydrates can also be applied to other water-containing materials, with a significant impact in many fields of materials science.
Subject(s)
Silicates , Water , Calcium Compounds , MineralsABSTRACT
Among the positive electrode materials for Na-ion batteries, Na3V2(PO4)2F3 is considered as one of the most promising and generates high interest. Here, we study the influence of the sol-gel synthesis parameters on the structure and on the electrochemical signature of the partially substituted Na3V2-zAlz(PO4)2(F,O)3 materials. We demonstrate that the acidity of the starting solution influences the vanadium oxidation state of the final product. For the first time we report on the possibility of controlling the double Al/V and O/F substitution that leads to the preparation of the Na3V2-zAlz(PO4)2F1+zO2-z solid solution.
ABSTRACT
We here present the synthesis of a new material, Na3(VO)Fe(PO4)2F2, by the sol-gel method. Its atomic and electronic structural descriptions are determined by a combination of several diffraction and spectroscopy techniques such as synchrotron X-ray powder diffraction and synchrotron X-ray absorption spectroscopy at V and Fe K edges, 57Fe Mössbauer, and 31P solid-state nuclear magnetic resonance spectroscopy. The crystal structure of this newly obtained phase is similar to that of Na3(VO)2(PO4)2F, with a random distribution of Fe3+ ions over vanadium sites. Even though Fe3+ and V4+ ions situate on the same crystallographic position, their local environment can be studied separately using 57Fe Mössbauer and X-ray absorption spectroscopy at Fe and V K edges, respectively. The Fe3+ ion resides in a symmetric octahedral environment, while the octahedral site of V4+ is greatly distorted due to the presence of the vanadyl bond. No electrochemical activity of the Fe4+/Fe3+ redox couple is detected, at least up to 5 V, whereas the reduction of Fe3+ to Fe2+ has been observed at â¼1.5 V versus Na+/Na through the insertion of 0.5 Na+ into Na3(VO)Fe(PO4)2F2. Comparing to Na3(VO)2(PO4)2F, the electrochemical profile of Na3(VO)Fe(PO4)2F2 in the same cycling condition shows a smaller polarization which could be due to a slight improvement in Na+ diffusion process thanks to the presence of Fe3+ in the framework. Furthermore, the desodiation mechanism occurring upon charging is investigated by operando synchrotron X-ray diffraction and operando synchrotron X-ray absorption at V K edge.
ABSTRACT
Layered oxide compositions Li3-xNaxNi2SbO6 have been prepared by solid-state synthesis. A complete solid solution is evidenced and characterized by X-ray and neutron diffraction as well as 7Li and 23Na solid-state nuclear magnetic resonance spectroscopy. The transition-metal layer is characterized by the classic honeycomb Ni2+/Sb5+ ordering, whereas a more uncommon randomly mixed occupancy of lithium and sodium is evidenced within the alkali interslab space. In situ X-ray diffraction and density functional theory calculations show that this alkali disordered feature is entropically driven. Fast cooling then appears as a synthesis root to confine bidimensional alkali glass within crystalline layered oxides.
ABSTRACT
Autoprotolysis of the metastable acid (C6F5)3BOPPh2OH, prepared in situ by the reaction of the rather weak Brønsted acid Ph2PO2H with the strong Lewis acid B(C6F5)3, gave rise to the formation of the eight-membered ring [Ph2POB(C6F5)2O]2 and C6F5H. The conjugate base was isolated as stable sodium crown ether salt [Na(15-crown-5)][Ph2PO2B(C6F5)3].
ABSTRACT
Although the electron-mediated spin-spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed "through-space" J couplings) have been reported. In this work, we investigate the observation of homonuclear 31P J couplings in organochalcogen heterocycles, which occur between 31P in two separate molecules, confirming without doubt their through-space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to 77Se. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.
ABSTRACT
Solid-state NMR spectra of new P-Se heterocycles based on peri-substituted naphthalene motifs show the presence of unusual J couplings between Se and P. These couplings are between atoms in adjacent molecules and occur "through space", rather than through conventional covalent bonds. Experimental measurements are supported by relativistic DFT calculations, which confirm the presence of couplings between nonbonded atoms, and provide information on the pathway of the interaction. This observation improves the understanding of J couplings and offers insight into the factors that affect crystal packing in solids, for future synthetic exploitation.
ABSTRACT
Three related series of peri-substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap = naphthalene-1,8-diyl N; Acenap = acenaphthene-5,6-diyl A; Aceyl = acenaphthylene-5,6-diyl Ay; Y = Ph 1; Fp 2; Tol 3; An-p- 4; An-o- 5; Tp 6; Mes 7; Tip 8) have been synthesised and their solid-state structures determined by X-ray crystallography. Molecular conformations were classified as a function of the two C9-C-Te-C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J((125)Te,(125)Te) spin-spin coupling constants between 3289-3848â Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt-type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050-2676â Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through-space coupling is supported by DFT calculations.
ABSTRACT
The series of eight 5-(TeY)-6-(SePh)acenaphthenes (Y = Fp (2), Tol (3), An-p (4), An-o (5), Tp (6), Mes (7), Tip (8), Nap (9)) were prepared and structurally characterised by X-ray crystallography, solution and solid-state NMR spectroscopy and density functional theory (DFT/B3LYP) calculations. All members of the series, except 5, adopt a BA type configuration comparable to the parent compound 1 (Y = Ph), aligning the Te-C(Y) bond along the mean acenaphthene plane and promoting a nonbonded Se···Te-C(Y) 3c-4e type interaction to form to stabilise the molecule (G-dependence). 5 (Y = An-o) adopts a BC type conformation in the solid but DFT calculations show this optimises to BA. Indication of strong through-space peri-interactions between Te and Se are observed in the (77)Se and (125)Te NMR spectra, with J(Te,Se) spin-spin coupling constants (SSCCs) in the range -688 to -748 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin-spin coupling on the same order of magnitude as observed in solution. In order to quantify the steric bulk of the aryl groups (Y), we introduce the crystallographic steric parameter (θ), the cone angle measured from the furthest H atoms lying on the edges of the cone to the Te atom located at its vertex. Modification to Y has no apparent influence over the conformation of the molecule, the degree of molecular distortion occurring in the acenaphthene backbone or the extent of 3c-4e interaction; peri-distances for all eight compounds are within 0.08 Å and no apparent correlation is observed between the steric bulk of Y (θ) and the (77)Se chemical shifts or J(Te,Se) SSCCs. In contrast, a good correlation is found between θ and (125)Te chemical shifts. DFT calculations performed on all members of the series confirm the comparable covalent bonding between Te and Se in the series, with WBIs of ca. 0.1 obtained. Natural bond orbital analysis shows a noticeable donor-acceptor interaction between a p-type lone pair on Se and a σ*(Te-C) antibonding orbital, confirming the onset of 3c-4e type bonding.
