Here we show for the first time a MOF that is photocatalytically active for light-assisted CO2methanation under mild conditions (215 °C), which can be further improved with the inclusion of metallic nanoparticles.
We have designed and synthesized eight isostructural 1D coordination polymers (CPs) with the general formula {[Ln(aapc)3(DMF)]}n [where Ln(iii) = Y (2), La (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9); and aapc = 3-((anthraquinone-1-yl)amino)propanoate]. These CPs consist of Ln-carboxylate infinite rods in which the bulky anthraquinone scaffolds arise from it in such a way that the resulting supramolecular packing exhibits isolated 1D chains. Solution structures have been corroborated through NMR methods including PGSE and EXSY NMR studies and, due to the presence of lanthanide ions, magnetic and luminescence properties have been studied. Alternating current magnetic measurements of compound 8 show slow relaxation of the magnetization, a characteristic of single molecule magnets (SMMs). The evaluation of solid-state photophysical properties reveals that the aapc scaffold sensitizes lanthanide(iii) based emission of compounds 4-9 both in the visible and near-infrared (NIR) regions at 10 K.
Detailed structural, magnetic, and photoluminescence (PL) characterization of four new compounds based on 1-methylimidazole-5-carboxylate (mimc) ligand and transition metal ions, namely [Ni(mimc)(HO)] (1), [Co(μ-mimc)] (2), {[Cu(μ-mimc)(HO)]·2HO} (3), and [Cd(μ-mimc)(HO)] (4) is reported. The structural diversity found in the family of compounds derives from the coordination versatility of the ligand, which coordinates as a terminal ligand to give a supramolecular network of monomeric entities in 1 or acts as a bridging linker to build isoreticular 2D coordination polymers (CPs) in 2-4. Magnetic direct-current (dc) susceptibility data have been measured for compounds 1-3 to analyze the exchange interactions among paramagnetic centers, which have been indeed supported by calculations based on broken symmetry (BS) and density functional theory (DFT) methodology. The temperature dependence of susceptibility and magnetization data of 2 are indicative of easy-plane anisotropy (D = +12.9 cm, E = +0.5 cm) that involves a bistable M = ±1/2 ground state. Alternating-current (ac) susceptibility curves exhibit field-induced single-ion magnet (SIM) behavior that occurs below 14 K, which is characterized by two spin relaxation processes of distinct nature: fast relaxation of single ions proceeding through multiple mechanisms (U = 26 K) and a slow relaxation attributed to interactions along the polymeric crystal building. Exhaustive PL analysis of compound 4 in the solid state confirms low-temperature phosphorescent green emission consisting of radiative lifetimes in the range of 0.25-0.43 s, which explains the afterglow observed during about 1 s after the removal of the UV source. Time-dependent DFT and computational calculations to estimate phosphorescent vertical transitions have been also employed to provide an accurate description of the PL performance of this long-lasting phosphor.
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