The influence of additives on the reaction kinetics and for microstructure refinement in LiBH 4-MgH 2 composites is investigated in detail. Indications on the rate limiting processes during the reactions are obtained by comparison of the measured reaction kinetics to simulations with one specific rate limiting process. The kinetics of the sorption reactions are derived from volumetric measurements as well as from in-situ Xray diffraction (XRD) measurements. During desorption, the hydrogen is released at a constant rate, which possibly is correlated to the one-dimensional growth of MgB 2 platelets. In contrast, the kinetic curves of the absorption reactions exhibit the typical shape of contracting-volume controlled kinetics. The microscopical interpretation of kinetic measurements are supported by transmission electron microscopy (TEM) images confirming the formation of additive-nanostructures in the grain boundaries upon cycling. The present investigations underline the importance of the additives as nucleation substrates and the influence of the microstructure on the reaction kinetics.

Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu 4 L 4 )(R/S-BINAPO) 4 , is assembled by four achiral C 3 -symmeric tris(βdiketones) (4,4′,4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)triphenylamine, L) as faces, four Eu(III) ions as vertices and four chiral R-/S-bis(diphenylphosphoryl)-1,1′-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu 4 L 4 )(R-BINAPO) 4 and (Eu 4 L 4 )(S-BINAPO) 4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |g lum | values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu(III) tetrahedral cages, ΔΔΔΔand ΛΛΛΛ-[(Eu 4 L 4 )(DPEPO) 4 ] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|g lum | = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties.

A durable bulk superhydrophobic film based on silicone rubber/silica was prepared by UV curing followed by solvent evaporation.

Because of the involvement of the gas–solid diffusion, device fabrication, and the relatively complex photophysical process, the lanthanide complexes are rarely exploited as fluorescence sensors for volatile compound (VC) detection. Herein, we report the first example of a discrete 3D Ln-based architecture as a sensor for VCs. The designed Eu4L4 tetrahedral cage shows highly selective, rapidly reversible, and turn-on emissive responses toward volatile amines/NH3 in a spin-coated film. Through the comprehensive spectral characteristic and density functional theory calculation, an intermolecular weak nucleophilic interaction is proposed for this response mechanism. Combining this weak interactions with the permeability of the cage, the film presents subsecond to second timescales rapid response; combining the fitting electrophilic capability of the β-diketonate units to amine nitrogen with the tunable intramolecular charge-transfer feature, the cage shows excellent selectivity and turn-on emissive response. This work provides a new clue to develop the lanthanide complexes as luminescence probes for VCs.

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