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A decomposition and self-assembly reaction affords a novel formyl iodoargentate [H 2 L] n [Ag 2 I 3 (μ-CHO)] n (1, L = 2,6-bis(1-imdazoly)pyridine) with an unprecedented CHO ? link mode, which provides the only example of iodoargentate incorporating the unstable formyl species under hydrothermal conditions. 1 exhibits luminescent and photocurrent response properties.

Two three-dimensional uranyl framework compounds consisting of 1,2,4-benzenetricarboxylic ligands and uranyl units have been synthesized under mild solvothermal conditions. Compound 1 adopts an open framework structure built from uranyl pentamers, which is a rare topology for uranyl structures. Compound 2 is constructed from UO 8 and UO 7 bipyramids that are connected by the ligand to form a three-dimensional framework. As a consequence, compound 1 exhibits an unusual photoluminescence spectrum of one broad peak at 545 nm with a significant red shift compared to the typical uranyl emissive peaks as shown in the spectra of uranyl nitrate and compound 2 . In addition, since compound 1 crystallizes in the noncentrosymmetric space group Cc , its secondary-harmonic generation property was measured under 1064 nm laser radiation, showing a moderate SHG signal response of 0.91 × KDP.

Four dinuclear bis(μ-Cl) bridged copper( II ) complexes, [Cu 2 (μ-Cl) 2 (L X ) 2 ](ClO 4 ) 2 (L X = N , N -bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H( 1 ), OMe( 2 ), Me( 3 ) and Cl( 4 )), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper( II ) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L X ligand , a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu( II ) site in its axial position forming an SP -I dinuclear Cu( II ) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1–3 exhibit methylmonooxygenase ( p MMO) behaviour and oxidise 4- tert -butylcatechol (4-TBCH 2 ) with molecular oxygen in MeOH or MeCN to 4- tert -butyl-benzoquinone (4-TBQ), 5-methoxy-4- tert -butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6′-Bu t -biphenyl-3,4,3′,4 ′ -tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Copper( I ) complexes featuring N-heterocyclic carbenes (NHCs) in which the nitrogen atoms are substituted by a 9-ethyl-9-fluorenyl group (EF) have been synthesised and tested in the hydrosylilation of functionalized and/or sterically demanding ketones and aldehydes. These reactions, carried out with triethylsilane as hydride source, were best achieved with the imidazolylidene copper complex 2d in which the EF substituents can freely rotate about the corresponding N–CEF bonds. The remarkable stability of the active species, which surpasses that of previously reported Cu–NHC catalysts is likely to rely on the ability of the NHC side arms to protect the copper centre during the catalytic cycle by forming sandwich-like intermediates, but also on its steric flexibility facilitating approach of encumbered substrates. TONs up to 1000 were reached.

A series of alkyltributylphosphonium chloride ionic liquids , prepared from tributylphosphine and the respective 1-chloroalkane, C n H 2 n +1 Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids , where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl)phosphonium chloride is detailed.

This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C–H bond for a more reactive C–metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C–H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)–(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules ( hydrides , oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds , ethers or alkenes ) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

Aluminum-based coordination polymers, MIL-110(Al) nanotubes, were successfully prepared from a mixed solution of methanol and ethanol with the volume ratio of 10?:?10 at room temperature in the absence of any template or surfactant; AlCl 3 and sodium 1,3,5-benzenetricarboxylate (Na 3 BTC) were employed as the initial reactants. The composition, structure, and morphology of the as-obtained nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). It was found that the initial reaction medium played a crucial role in the formation of nanotubes. More importantly, MIL-110(Al) nanotubes could be fabricated into lanthanide-functionalized luminescent materials by a simple post-treatment process. The as-obtained luminescent materials could emit red, green, and white light, which have potential applications in the fields of sensing, biomedicine, labeling, and color display. Furthermore, the PL of the as-obtained luminescent materials could be selectively quenched by Fe 3+ ions, which can be used as probes for the detection of Fe 3+ ions.

Amorphization is considered to be an effective way to enhance the electrochemical performances of electrode materials due to the existence of isotropy and numerous defects. Herein, an amorphous hierarchically structured MnO 2 /acetylene black (a-MnO 2 /AB) composite is successfully fabricated via a redox method and subsequent mechanical ball milling. The a-MnO 2 /AB composite is composed of approximately 300 nm flower-like amorphous MnO 2 submicron spheres and acetylene black particles with a diameter of about 50 nm. The a-MnO 2 /AB electrode exhibits an initial coulombic efficiency of 73.2%, excellent rate capabilities of 318 mA h g ?1 at 9.6 A g ?1 , and high specific capacity retention of 1300 mA h g ?1 after 300 cycles at 1 A g ?1 . The amorphous structure can provide more channels for rapid lithium-ion transmission due to the disorder and defects, and the ion-diffusion coefficient (～5 × 10 ?7 cm 2 s ?1 ) is higher than those of crystalline materials. Due to the strong interactions (Mn–O–C bonds) between MnO 2 and AB as a result of the ball milling, the composite shows low charge transport resistance and small volume changes during the discharging/charging process. This work provides a facile route for the construction of amorphous hierarchically structured Mn-based oxides as anodes for lithium-ion batteries (LIBs).

The fabrication of SnO x in thin film form via chemical solution deposition (CSD) processes is favored over vacuum based techniques as it is cost effective and simpler. The precursor employed plays a central role in defining the process conditions for CSD. Particularly for processing SnO 2 layers that are appealing for sensor or electronic applications, there are limited precursors available for CSD. Thus the focus of this work was to develop metalorganic precursors for tin, based on the ketoiminate ligand class. By systematic molecular engineering of the ligand periphery, a series of new homoleptic Sn( II ) β-ketoiminate complexes was synthesized, namely bis[4-(2-methoxyethylimino)-3-pentanonato] tin, [Sn(MEKI) 2 ] ( 1 ), bis[4-(2-ethoxyethylimino)-2-pentanonato] tin, [Sn(EEKI) 2 ] ( 2 ), bis[4-(3-methoxypropylimino)-2-pentanonato] tin, [Sn(MPKI) 2 ] ( 3 ), bis[4-(3-ethoxypropylimino)-2-pentanonato] tin, [Sn(EPKI) 2 ] ( 4 ) and bis[4-(3-isopropoxypropylimino)-2-pentanonato] tin, [Sn( i PPKI) 2 ] ( 5 ). All these N-side-chain ether functionalized compounds were analyzed by nuclear magnetic resonance (NMR) spectroscopy, electron impact mass spectrometry (EI-MS), elemental analysis (EA) and thermogravimetric analysis (TGA). The solid state molecular structure of [Sn(MPKI) 2 ] ( 3 ) was eludicated by means of single crystal X-ray diffraction (SCXRD). Interestingly, this class of compounds features excellent solubility and stability in common organic solvents alongside good reactivity towards H 2 O and low decomposition temperatures, thus fulfilling the desired requirements for CSD of tin oxides. With compound 3 as a representative example, we have demonstrated the possibility to directly deposit SnO x layers via hydrolysis upon exposure to air followed by heat treatment under oxygen at moderate temperatures and most importantly without the need for any additive that is generally used in CSD. A range of complementary analytical methods were employed, namely X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to analyse the structure, morphology and composition of the SnO x layers.

A chiral, tetradentate polyether ligand with a trans -1,2-cyclohexanediyl backbone, bis(methoxyethoxy)- trans -1,2-cyclohexane ( 5 ), was synthesized as both a racemate and the ( S , S ) enantiomer. 5 was found to form stable adducts with alkaline earth metal amides [M{N(SiMe 3 ) 2 } 2 (thf) x ] (M = Mg ( x = 0), Ca ( x = 2) and Sr ( x = 2/3)), [Ca{N(SiHMe 2 ) 2 } 2 (thf)] as well as with hydrocarbyl compounds [Mg(CH 2 SiMe 3 ) 2 ] and [Ca(η 3 -C 3 H 5 ) 2 ]. X-ray diffraction study of the bis(amide) [(( S , S )- 5 )Ca{N(SiMe 3 ) 2 } 2 ] and of the bis(allyl) [( rac - 5 )Ca(η 3 -C 3 H 5 ) 2 ] was performed. The complexes obtained were tested as initiators for the ring-opening polymerization of meso -, racemic and L -lactide.