Notes

Twin mechanoluminescence method composed of a new solid-state di-copper(We) complicated that contain N-heterocyclic carbene ligands.
Although the underlying B-site cations are well-known active sites, this is the first demonstration of A(Pr3+)-site cations influencing the activity by reversibly altering their oxygen coordination. see more Higher Co-doping thwarts the NS formation, affecting the catalytic performance. The facile OER/ORR activity of the thickness-tunable NSs has larger implications as a bifunctional air-electrode material for metal-air batteries and fuel cells.The inverse electron-demand Diels-Alder (IEDDA) pyridazine elimination is one of the key bioorthogonal bond-breaking reactions. In this reaction trans-cyclooctene (TCO) serves as a tetrazine responsive caging moiety for amines, carboxylic acids and alcohols. One issue to date has been the lack of synthetic methods towards TCO ethers from functionalized (aliphatic) alcohols, thereby restricting bioorthogonal utilization. Two novel reagents were developed to enable controlled formation of cis-cyclooctene (CCO) ethers, followed by optimized photochemical isomerization to obtain TCO ethers. The method was exemplified by the controlled bioorthogonal activation of the lac operon system in E. coli using a TCO-ether-modified carbohydrate inducer.The dodecanuclear coordination cage [Cd12(Lnaph)12(Lmes)4](BF4)24 consists of a set of four triangular, trinuclear helical panels Cd3(μ-Lnaph)36+ (based on ditopic bridging ligands Lnaph), which are connected by four tritopic ligands Lmes. The result is that the four triangular helical panels and the four Lmes-capped triangular faces of the cuboctahedral core form two alternating subsets of the eight triangular faces of the cuboctahedron. Crystallographic investigations revealed that the triangular helicate faces can have 'clockwise' (C) or 'anticlockwise' (A) helicity, and that the helicity of each face can vary independently of the others as they are mechanically separated. This generates a set of three diastereoisomers in which all four cyclic helicate faces in the cuboctahedron have the same chirality (AAAA/CCCC enantiomers with T symmetry; AAAC/CCCA enantiomers with C 3 symmetry; and achiral AACC with S 4 symmetry). This mirrors the known behaviour of many simpler M4L6 tetrahedral cages which can likewise exist as T, C 3 or S 4 isomers according to the sense of tris-chelate chirality around each individual metal centre but here it is translated onto a much larger scale by the four chiral units being entire trinuclear helicate faces rather than single metal centres. 1H NMR spectroscopy confirms the presence of the three diastereoisomers with their different molecular symmetries in a ratio slightly different from what is expected on purely statistical grounds; and 1H NMR measurements on a non-equilibrium sample (enriched by manual crystal-picking before preparing the solution) showed that the distribution does not change over several weeks in solution, indicating the kinetic inertness of the cage assemblies.The Simmons-Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal-carbon multiple bonds. Herein, we describe this type of reaction and the construction of three-membered rings has now been applied in organometallic systems by combining classical zinc carbenoid reagents with a range of structurally and electronically diverse metal carbynes. A variety of metallacyclopropene derivatives prepared in this way represent rare examples with σ-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations.Iridium has played an important role in the evolution of C-H activation chemistry over the last half century owing to its high reactivity towards stoichiometric C-H bond cleavage; however, the use of Ir(iii) complexes in catalytic C-H functionalization/C-C bond formation appears to have fallen off significantly. The main problem lies in the reductive elimination step, as iridium has a tendency to form stable and catalytically inactive Ir(iii) species. Herein, with a rationally designed Lewis acid assisted oxidatively induced strategy, the sluggish Ir(iii) reductive elimination is successfully facilitated, enabling the facile C-C bond formation. The X-ray crystal structure of a silver salt adduct of iridacycle and DFT calculations demonstrate that the sulfoxide group acts as a key bridge connecting the Ir(iii) metal centre with the silver Lewis acid, which facilitates the reductive elimination of the Ir(iii) metallacycle. Further identification of oxidants was carried out by performing stoichiometric reactions, which enables the development of catalytic construction of various highly functionalized seven-membered-ring sulfoxides, that are of great interest in medicinal chemistry and materials science.Based upon the hetero-N,O ligand of pyrimidine-5-carboxylic acid (Hpmc), a new semiconductive Cu(i)/Cu(ii) mixed-valence MOF with the full light spectrum and a novel topology of 43·612·86243·63263664·823, (Cu4I4)2.5[Cu3(μ4-O) (μ3-I) (pmc)3(Dabco)3]·2.5DMF·2MeCN∞ (NJU-Bai61, NJU-Bai for Nanjing University Bai group; Dabco = 1,4-diazabicyclo [2.2.2] octane), was synthesized stepwise. NJU-Bai61 exhibits good water/pH stabilities and a relatively large CO2 adsorption capacity (29.82 cm3 g-1 at 1 atm, 273 K) and could photocatalyze the reduction of CO2 into CH4 without additional photosensitizers and cocatalysts and with a high CH4 production rate (15.75 μmol g-1 h-1) and a CH4 selectivity of 72.8%. The CH4 selectivity is the highest among the reported MOFs in aqueous solution. Experimental data and theoretical calculations further revealed that the Cu4I4 cluster may adsorb light to generate photoelectrons and transfer them to its Cu3OI(CO2)3 cluster, and the Cu3OI(CO2)3 cluster could provide active sites to adsorb and reduce CO2 and deliver sufficient electrons for CO2 to produce CH4. This is the first time that the old Cu(i) x X y L z coordination polymers' application has been extended for the photoreduction of CO2 to CH4 and this opens up a new platform for the effective photoreduction of CO2 to CH4.
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