The peculiar mechanism of cooperative CO₂ adsorption in a perfluorinated Ce^IV-based metal–organic framework with MIL-140 topology is disclosed using a combination of experimental and computational methods.

The characterization of the structural and dynamic properties of rubber networks is of fundamental importance in rubber science and technology to design materials with optimized mechanical properties. In this work, natural and isoprene rubber networks obtained by curing at three different temperatures (140, 150, and 170 °C) and three different sulfur contents (1, 2, and 3 phr) in the presence of a 3 phr accelerator were studied using a combination of low-field time-domain NMR (TD-NMR) techniques, including ¹H multiple-quantum experiments for the measurement of residual dipolar couplings (D_res), the application of the Carr–Purcell–Meiboom–Gill pulse sequence for the measurement of the transverse magnetization decay and the extraction of ¹H T₂ relaxation times, and the use of field cycling NMR relaxometry for the determination of T₁ relaxation times. The microscopic properties determined by TD-NMR experiments were discussed in comparison with the macroscopic properties obtained using equilibrium swelling, moving die rheometer, and calorimetric techniques. The obtained correlations between NMR observables, crosslink density values, maximum torque values, and glass transition temperatures provided insights into the effects of the vulcanization temperature and accelerator/sulfur ratio on the structure of the polymer networks, as well as on the effects of crosslinking on the segmental dynamics of elastomers. D_res and T₂ were found to show linear correlations with the crosslink density determined by equilibrium swelling, while T₁ depends on the local dynamics of polymer segments related to the glass transition, which is also affected by chemical modifications of the polymer chains occurring during vulcanization.

The encapsulation of [Eu(dbm)₃phen] into functionalized mesoporous silica nanoparticles (MSN) has been carried out to study the effect of chemical environments on the photoluminescence properties of the rare-earth complex. Surface functionalization was achieved by the reaction of the silanol groups on the surface of mesoporous silica with different organosilylating agents such as (3-aminopropyl)-triethoxysilane (APTES), (3-mercaptopropyl)-trimethoxysilane (MPTMS), and ethoxytrimethylsilane (ETMS). A change in the luminescence properties of the Eu(dbm)₃phen complex has been observed on its encapsulation into surface modified mesoporous silica nanoparticles. The modification of photophysical properties is attributed to the interaction of Eu(dbm)₃phen with the different chemical environments in the functionalized mesoporous silica nanoparticles (MSN). The luminescence properties of the rare-earth complex in surface-modified MSN increase in the order MSN < MSN–ETMS < MSN–MPTMS < MSN–APTES. The Eu(dbm)₃phen complex encapsulated in the functionalized mesoporous silica nanoparticles shows an enhanced luminescence and an increased lifetime compared to the pure rare-earth complex in the solid state and that in unmodified MSN. This implies that some interactions of the lanthanide complexes take place during their incorporation process into the organically modified mesoporous silica nanoparticles. The organically modified mesoporous silica nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR) and N₂ adsorption desorption measurements. The luminescence properties of the encapsulated Eu(dbm)₃phen were studied in detail. Moreover, the effect of functionalized MSNs on the structural behaviour of the Eu(dbm)₃phen was investigated by solid state nuclear magnetic resonance (SSNMR) techniques using an analogous diamagnetic model complex, Y(dbm)₃phen, encapsulated into functionalized MSNs. These studies indicate that the encapsulated rare-earth complex shows some interactions with the functional groups anchored on the surface of MSNs.

The chemical functionalization of 2D exfoliated black phosphorus (2D BP) continues to attract great interest, although a satisfactory structural characterization of the functionalized material has seldom been achieved. Herein, we provide the first complete structural characterization of 2D BP functionalized with rare discrete Pd₂ units, obtained through a mild decomposition of the organometallic dimeric precursor [Pd(η³-C₃H₅)Cl]₂. A multitechnique approach, including HAADF-STEM, solid-state NMR, XPS, and XAS, was used to study in detail the morphology of the palladated nanosheets (Pd₂/BP) and to unravel the coordination of Pd₂ units to phosphorus atoms of 2D BP. In particular, XAS, backed up by DFT modeling, revealed the existence of unprecedented interlayer Pd–Pd units, sandwiched between stacked BP layers. The preliminary application of Pd₂/BP as a catalyst for the hydrogen evolution reaction (HER) in acidic medium highlighted an activity increase due to the presence of Pd₂ units.