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Abstract: Kinetics of ring-opening metathesis polymerization (ROMP) of exo,exo-5,6-di(methoxycarbonyl)-7-oxabicyclo[2.2.1]hept-2-ene, promoted by the Grubbs’ 1st generation precatalyst, has been effectively monitored by FT-Raman and NMR spectroscopy. Both techniques evidenced similar monomer conversions to be attained under the same reaction conditions. The present FT-Raman study provided information on the polymer steric configuration, the Raman bands at 1670 and 1677cm−1 being specifically assigned to stretching vibrations of double bonds from the cis- and trans-polymer, respectively. The trans/cis ratio observed by FT-Raman parallels the corresponding result from 1H NMR. For the first time, a comparison was made on application of these complementary methods on the same ROMP reaction, evidencing their assets and disadvantages and reliability of FT-Raman. [Copyright &y& Elsevier]

In view of Hg 2+ ion sensing by luminescence, a series of new, phenanthroline-decorated 3D lanthanide metal organic frameworks (Ln-MOFs) valorising an original combination of four different lanthanides and two organic ligands, i.e. thiobis(4-methylene-benzoic acid) (H 2 tmba) and 1,10-phenanthroline (phen), have been successfully synthesized, namely {[Ln 4 (tmba) 6 (phen) 4 ]· m (H 2 O)(phen)} n [Ln = Ce, m = 3 (1); Pr, m = 1 (2); Eu, m = 3 (3); and Tb, m = 3 (4)]. Compounds 1-4 were characterised by single-crystal X-ray diffraction, elemental and thermogravimetric analyses, and powder X-ray diffraction. The luminescence properties of complexes 3 and 4 were thoroughly investigated. It is herein proved that compound 3 sensitively and selectively acts as an excellent luminescent probe for the detection of Hg 2+ ions in waters, with a detection limit of 1.00 μM. As additional assets, 3 displays superb stability over a wide pH range (3-12) of the aqueous media, as well as convenient recycling after completion of the detection experiments. The rationale for the observed luminescence quenching effect of mercury might be a strong interaction arising between Hg 2+ ions and the carboxylate oxygen atoms of the tmba 2- ligand. The results open new perspectives for applications in environmental remediation.

The generation of hydrogen-based energy and environmental remediation using sunlight is an emerging topic of great significance for meeting the ever-growing global need. However, the actual photocatalytic performance is still far below expectations because of the relatively slack charge-carrier separation and migration as well as insufficient spectral absorption in semiconductors. Therefore, the rational construction of heterojunctions is considered as an effective approach to solving the above issues. In this context, we have, for the first time, designed and synthesized a two-dimensional 2D-on-2D heterostructure, based on 2D Ag-doped ZnIn 2 S 4 nanoplates deposited on 2D g-C 3 N 4 nanosheets (denoted as g-C 3 N 4 /Ag:ZnIn 2 S 4 ). This construct benefits from improved visible-light absorption by unveiling a greater number of catalytically active sites, effectively enhancing charge-carrier separation and relocation. Detailed analysis has proved that under visible-light irradiation, the optimized g-C 3 N 4 /20 wt% Ag:ZnIn 2 S 4 nanocomposite has substantially upgraded photocatalytic activity in hydrogen formation by water splitting (hydrogen evolution rate of up to 597.47 μmol h -1 g -1 ) and in residual dyestuff degradation (methyl orange, MO; degradation rate constant of 0.1406 min -1 ). Noteworthily, these two exceptionally high values respectively represent 30.73 and 5.42 times enhancements vs. results obtained with bare g-C 3 N 4 . Another strong point of our g-C 3 N 4 /Ag:ZnIn 2 S 4 is its impressive recyclability for 20 runs, with no relevant metal release in the aqueous solution following photocatalysis. This work introduces new, superior access to highly efficient photocatalysts founded on 2D/2D nanocomposites serving both the production of hydrogen as an energy carrier and environmental remediation., Competing Interests: The authors declare no competing interest., (This journal is © The Royal Society of Chemistry.)

Pd nanoparticles were immobilized on a highly porous, hydrothermally stable Eu-MOF via solution impregnation and H2 reduction to yield a novel Pd@Eu-MOF nanocatalyst. This composite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS). Unprecedentedly, the Pd@Eu-MOF nanocatalyst could be applied with excellent results in two strikingly different, mechanistically distinct, reactions i.e., Suzuki-Miyaura cross-coupling and cycloaddition of CO2 to a range of epoxides. Under the best reaction conditions, 98-99% yields have been attained in both catalytic processes. Moreover, in either case the heterogeneous catalyst was easily recovered and efficiently reused for more than four cycles, indicating its high stability and reproducibility. PXRD, TEM and XPS measurements on the recycled catalyst confirmed that it maintained its original structure and morphology; no Pd NP agglomeration was observed.

An easy access to a series of previously unreported heterodinuclear Pd-Ln compounds, Pd-bpydc-La, Pd-bpydc-Ce and Pd-bpydc-Nd (bpydc = 2,2'-bipyridine-5,5'-dicarboxylate) has been developed. The Pd-Ln hybrid networks were effectively applied as catalysts in Suzuki⁻Miyaura C-C cross-coupling reactions of 4-bromoanisole and 4-bromobenzonitrile with phenylboronic acid, under mild conditions. A systematic investigation revealed Pd-bpydc-Nd as the most active catalyst. In all cases, reaction yields varied with the base, catalyst loading and substantially augmented with temperature (from 30 to 60 °C). Substituent effects were operative when changing from 4-bromoanisole to 4-bromobenzonitrile. The key role played by the lanthanides, aromatic substrate and base, in modulating the Pd-catalytic cycle has been highlighted. Importantly, the new catalysts proved to be stable in air and vs . functionalities and are quite efficient in Suzuki⁻Miyaura carbon-carbon bond formation conducted in protic solvents., Competing Interests: The authors declare no conflict of interest.