All-boron analogues of aromatic hydrocarbons: B17- and B18-

We have investigated the structural and electronic properties of the B(17)(-) and B(18)(-) clusters using photoelectron spectroscopy (PES) and ab initio calculations. The adiabatic electron detachment energies of B(17)(-) and B(18)(-) are measured to be 4.23 ± 0.02 and 3.53 ± 0.05 eV, respectively. Calculated electron detachment energies are compared with experimental data, confirming the presence of one planar C(2v) ((1)A(1)) isomer for B(17)(-) and two nearly isoenergetic quasi-planar C(3v) ((2)A(1)) and C(s) ((2)A') isomers for B(18)(-). The stability and planarity/quasi-planarity of B(17)(-) and B(18)(-) are ascribed to σ- and π-aromaticity. Chemical bonding analyses reveal that the nature of π-bonding in B(17)(-) and B(18)(-) is similar to that in the recently elucidated B(16)(2-) and B(19)(-) clusters, respectively. The planar B(17)(-) cluster can be considered as an all-boron analogue of naphthalene, whereas the π-bonding in the quasi-planar B(18)(-) is reminiscent of that in coronene.     

Metal-free inorganic ligands for colloidal nanocrystals: S2-, HS-, Se2-, HSe-, Te2-, HTe-, TeS3(2-), OH-, and NH2- as surface ligands

All-inorganic colloidal nanocrystals were synthesized by replacing organic capping ligands on chemically synthesized nanocrystals with metal-free inorganic ions such as S(2-), HS(-), Se(2-), HSe(-), Te(2-), HTe(-), TeS(3)(2-), OH(-) and NH(2)(-). These simple ligands adhered to the NC surface and provided colloidal stability in polar solvents. The versatility of such ligand exchange has been demonstrated for various semiconductor and metal nanocrystals of different size and shape. We showed that the key aspects of Pearson's hard and soft acids and bases (HSAB) principle, originally developed for metal coordination compounds, can be applied to the bonding of molecular species to the nanocrystal surface. The use of small inorganic ligands instead of traditional ligands with long hydrocarbon tails facilitated the charge transport between individual nanocrystals and opened up interesting opportunities for device integration of colloidal nanostructures.     

Efficient electron transfer through a triazole link in ruthenium(II) polypyridine type complexes

Spectroscopic, electrochemical and theoretical characterisations of photoactive systems readily assembled via click-chemistry show an efficient bi-directional charge shift through the triazole link.     

Improved sulfuric acid decrystallization of wheat straw to obtain high yield carbohydrates

Wheat straw is an abundant residue of agriculture which is increasingly considered as a feedstock for the production of fuels, energy and chemicals. The concentrated acid hydrolysis of wheat straw has been investigated in this work. Hemicellulose and cellulose have been efficiently converted into monomers of pentoses and glucose in high yields by a one-pot decrystallization-hydrolysis procedure. This process differs from usual concentrated acid biomass fractionation methodologies as a low quantity of acid is used and the supplementary use of a costly acid is not necessary to yield efficiently carbohydrates. The influence of the acid native concentration, and of the time of the decrystallization step have been studied so as to optimise yields of carbohydrates using a minimum of sulfuric acid so as to preserve a potential market value of the process. One can also imagine that this procedure will not impact dramatically the subsequent purification costs. In view of the growing importance of renewable resource-based molecules in the chemical industry, and the necessity to produce fermentable substrate for biofuels, this approach may open a new avenue for the use of wheat straw as raw material for various applications.     

Synthesis and structural aspects of N-triflylphosphoramides and their calcium salts--highly acidic and effective Brønsted acids

Recently, 1,1′‐bi‐2‐naphthol (BINOL)‐based N‐triflylphosphoramides emerged as a new class of potent Brønsted acid catalysts. In this paper we describe the efficient synthesis of various BINOL‐based N‐triflylphosphoramides and their calcium salts. Furthermore, X‐ray crystal structure analysis combined with energy‐dispersive X‐ray spectroscopy (EDX) measurements confirmed that the synthesised chiral N‐triflylphosphoramides are highly acidic metal‐free catalysts.     

Methyl 3‐(4‐methoxyphenyl)prop‐2‐enoate

The title mol­ecule, C₁₁H₁₂O₃, is almost planar, with an average deviation of the C and O atoms from the least‐squares plane of 0.146 (4) Å. The geometry about the C=C bond is trans. The phenyl ring and –COOCH₃ group are twisted with respect to the double bond by 9.3 (3) and 5.6 (5)°, respectively. The endocyclic angle at the junction of the propenoate group and the phenyl ring is decreased from 120° by 2.6 (2)°, whereas two neighbouring angles around the ring are increased by 2.3 (2) and 0.9 (2)°. This is probably associated with the charge‐transfer interaction of the phenyl ring and –COOCH₃ group through the C=C double bond. The mol­ecules are joined together through C—H?O hydrogen bonds between the methoxy and ester groups to form characteristic zigzag chains extended along the c axis.     

Ba(SbF(6))(2).5XeF(2): first xenon(II) compound with barium. Synthesis,vibrational spectra,and crystal structure

The reaction between Ba(SbF(6))(2) and excess XeF(2) in anhydrous HF at room temperature yields the white solid Ba(SbF(6))(2).5XeF(2) after the excess XeF(2) and the solvent have been removed under vacuum. Ba(SbF(6))(2).5XeF(2) crystallizes in the monoclinic space group C2/m, with a = 13.599(6) A, b = 12.086(4) A, c = 9.732(5) A, beta = 134.305(6) degrees, V = 1144.7 (8) A(3), and Z = 2. The coordination sphere of each barium atom consists of 12 fluorine atoms. The structure consists of alternating layers of Ba(SbF(6))(2).XeF(2) and 4 XeF(2) molecules. The Ba atoms in the Ba(SbF(6))(2).XeF(2) layer are in a nearly rhombic-net array and are linked with trans F-bridging ligands of SbF(6)(-). A XeF(2) molecule is placed in the center of each rhombus of the Ba(2+) array so that its symmetry axis is perpendicular to the plane of the Ba(SbF(6))(2).XeF(2) layer. This layer is linked to its neighbors by a layer of centrosymmetric XeF(2) molecules. Raman spectra are in accord with all XeF(2) molecules being symmetrical.     

Synthesis of photochromic 1,2-dihetarylethene using regioselective acylation of thienopyrroles

[formula: see text] The influence of catalysts, acid chlorides, and solvents in the acylation of methyl 2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate was studied. Conditions for the regioselective acylation processes were found. Thienopyrrole-based photochrome was synthesized for the first time.     

Hetero‐Multifunctional Poly(ethylene glycol) Copolymers with Multiple Hydroxyl Groups and a Single Terminal Functionality

Hetero‐multifunctional poly(ethylene glycol‐co‐glycerol) random copolymers with multiple hydroxyl functionalities and a single terminal functionality have been prepared by copolymerization of ethylene oxide (EO) and ethoxy ethyl glycidyl ether (EEGE) with the use of a suitable initiator, introducing a protected amino group or a double bond, respectively. Acidic deprotection was used for removal of the acetal protecting groups in the chain, and the terminal amino group was regenerated by catalytic hydrogenation. A series of copolymers with narrow polydispersity was obtained, varying comonomer fractions from 3 to 67% and molecular weights in the range of 5 000–32 000 g · mol⁻¹ (1.05 < < 1.25). Molecular and thermal characterization was carried out using ¹H‐ and ¹³C NMR, SEC and differential scanning calorimetry (DSC).