Template-aluminosilicate structures at the early stages of zeolite ZSM-5 formation. A combined preparative, solid-state NMR, and computational study

Species at three stages in the self-assembly of zeolite ZSM-5 have been studied with one- and two-dimensional magic-angle-spinning 13C, 27Al, 29Si, and 1H NMR spectroscopy and compared with the earlier proposed structures: (1) precursor species containing 33-36 T sites around a tetrapropylammonium (TPA) cation, (2) nanoslabs consisting of a flat 4 x 3 array of such precursors, and (3) the final TPA-ZSM-5 zeolite. Synthesis was carried out in D2O to suppress the water and silanol protons. Under such conditions, the effective Si-H and Al-H distances measured with 29Si-{1H} and 27Al-{1H} rotational echo double resonance (REDOR) reflect the interactions between TPA cations and the surrounding aluminosilica. The 29Si-{1H} REDOR curves for Q4-type silicon atoms at the three mentioned stages are closely similar, as well as the observed 27Al-1H REDOR curve for the precursor species compared to that for the TPA-ZSM-5. This indicates that in addition to externally attached TPA, there is also internal TPA already incorporated at an early stage into the aluminosilicate in a similar way as in the final zeolite, in accordance with the earlier proposed MFI self-assembly pathway (Kirschhock et al. Angew. Chem. Int. Ed. 2001, 40, 2637). However, the effective distances extracted from the initial REDOR curvatures are significantly (10-15%) larger than those computed for the model. Since there is no temperature effect, we tentatively assign this difference to a reduction of the 29Si-1H and 27Al-1H interactions by multispin decoherence effects or self-decoupling caused by proton spin diffusion. By assuming the computed model distances and fitting Anderson-Weiss curves to the observed REDOR data, we obtain similar "decoherence times" in the order of 0.1 ms. The observed 29Si-{1H} REDOR dephasing for the Q3 sites in the precursors is significantly faster than that for the Q4 sites. This is tentatively ascribed to a partial deuteron-proton back exchange at the silanol positions.     

Stepwise noncovalent synthesis leading to dendrimer-based assemblies in water

We provide detailed insight into complex supramolecular assembly processes by fully characterizing a multicomponent model system using dynamic light scattering, cryogenic transmission electron microscopy, atomic force microscopy, and various NMR techniques. First, a preassembly of a host molecule (the fifth-generation urea-adamantyl poly(propylene imine) dendrimer) and 32 guest molecules (a water- and chloroform-soluble ureidoacetic acid guest) was made in chloroform. The association constant in chloroform is concealed by guest self-association and is therefore higher than 10(3) M(-1). Via the neat state the single-host complex was transferred to water, where larger dendrimer-based assemblies were formed. The core of these assemblies, consisting of multiple host molecules (on average three), is kinetically trapped upon dissolution in water, and its size is constant irrespective of the concentration. The guest molecules forming the corona of the assemblies, however, stay dynamic since they are still in rapid exchange on the NMR time scale, as they were in chloroform. A stepwise noncovalent synthesis provides a means to obtain metastable dynamic supramolecular assemblies in water, structures that cannot be formed in one step.     

Lightweight hydrogen-storage material Mg(0.65)Sc(0.35)D2 studied with 2H and 2H-{45Sc} MAS NMR exchange spectroscopy

Using double-quantum (2)H MAS NMR with (45)Sc recoupling and Bloch-Siegert compensated (2)H-{(45)Sc} TRAPDOR we have identified the overlapping NMR signals of deuterium with and without scandium neighbors in Mg(0.65)Sc(0.35)D(2), a candidate lightweight material for hydrogen storage. At room temperature we also observe a third type of mobile deuterium. Deuterium mobility among the three NMR-distinct sites has been investigated by means of one-and two-dimensional exchange spectroscopy (Exsy). Complete deuterium exchange within 0.1s is observed, which indicates that the three NMR-distinct sites are close together in the crystal lattice. The weak temperature- and MAS-rate dependences observed in Exsy are indicative for a combination of chemical exchange and spin diffusion.     

Study of DyFe12−xMx compounds by57Fe and161Dy Mössbauer spectroscopy

DyFe_12?xM_x (M=Si,Ti,Cr) were studied with⁵⁷Fe and¹⁶¹Dy Mössbauer spectroscopy. The deduced coupling constants J_RFe of these compounds are about equal. It is found that Si is substituting one particular Fe-site, while Cr is substituting Fe randomly. In DyFe₁₀Si₂ two Fe-sites favour a c-axis anisotropy, while the third one favours the basal plane.     

Surface modification of oxidic nanoparticles using 3-methacryloxypropyltrimethoxysilane

Tin oxide, antimony-doped tin oxide (ATO), and silica nanosized particles in aqueous dispersion were reacted with various amounts of 3-methacryloxypropyltrimethoxysilane (MPS). The kinetics were followed by 29Si NMR and the products were analyzed by FTIR and 29Si NMR. The kinetic experiments on ATO and silica revealed that the hydrolysis is the rate-determining step in these reactions. The reaction of MPS with the particles is favored over the homocondensation of MPS. Quantitative analysis using FTIR revealed that the amount of MPS grafted onto the tin oxide and silica particles is limited to the amount needed to fill one monolayer. For ATO the maximum amount of grafted MPS was only 50-70% of the amount that is needed for a closed monolayer. The MPS molecules are for the most part oriented parallel to the oxide surface, and a hydrogen bond between the MPS-carbonyl and the oxide is formed.     

[Ge2]4− Dumbbells with Very Short Ge−Ge Distances in the Zintl Phase Li3NaGe2: A Solid‐State Equivalent to Molecular O2

The novel ternary Zintl phase Li₃NaGe₂ comprises alkali‐metal cations and [Ge₂]^4? dumbbells. The diatomic [Ge₂]^4? unit is characterized by the shortest Ge?Ge distance (2.390(1) Å) ever observed in a Zintl phase and thus represents the first Ge=Ge double bond under such conditions, as also suggested by the (8?N) rule. Raman measurements support these findings. The multiple‐bond character is confirmed by electronic‐structure calculations, and an upfield ⁶Li NMR shift of ?10.0 ppm, which was assigned to the Li cations surrounded by the π systems of three Ge dumbbells, further underlines this interpretation. For the unperturbed, ligand‐free dumbbell in Li₃NaGe₂, the π‐ bonding p_y and p_z orbitals are degenerate as in molecular oxygen, which has singly occupied orbitals. The partially filled π‐type bands of the neat solid Li₃NaGe₂ cross the Fermi level, resulting in metallic properties. Li₃NaGe₂ was synthesized from the elements as well as from binary reactants and subsequently characterized crystallographically.