The Role of MgCl2 as a Lewis Base in ROMgCl-MgCl2 Electrolytes for Magnesium-Ion Batteries.

A series of strong Lewis acid-free alkoxide/siloxide-based Mg electrolytes were deliberately developed with remarkable oxidative stability up to 3.5 V (vs. Mg/Mg(2+)). Despite the perception of ROMgCl (R=alkyl, silyl) as a strong base, ROMgCl acts like Lewis acid, whereas the role of MgCl2 in was unambiguously demonstrated as a Lewis base through the identification of the key intermediate using single crystal X-ray crystallography. This Lewis-acid-free strategy should provide a prototype system for further investigation of Mg-ion batteries.

Cascade synthesis of a gold nanoparticle-network polymer composite.

The multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4](-). The reaction sequence begins with the auto-reduction of aqueous [AuCl4](-) by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate end-derivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4](-), formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multi-lamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Optical spectroscopy shows a notable red shift (Δλ ∼ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.

Effects of electronegative substitution on the optical and electronic properties of acenes and diazaacenes.

Large acenes, particularly pentacenes, are important in organic electronics applications such as thin-film transistors. Derivatives where CH units are substituted by sp(2) nitrogen atoms are rare but of potential interest as charge-transport materials. In this article, we show that pyrazine units embedded in tetracenes and pentacenes allow for additional electronegative substituents to induce unexpected redshifts in the optical transitions of diazaacenes. The presence of the pyrazine group is critical for this effect. The decrease in transition energy in the halogenated diazaacenes is due to a disproportionate lack of stabilization of the HOMO on halogen substitution. The effect results from the unsymmetrical distribution of the HOMO, which shows decreased orbital coefficients on the ring bearing chlorine substituents. The more strongly electron-accepting cyano group is predicted to shift the transitions of diazaacenes even further to the red. Electronegative substitution impacts the electronic properties of diazaacenes to a much greater degree than expected.

Water-soluble benzo- and naphtho-thiadiazole-based bistriazoles and their metal-binding properties.

A click reaction furnishes water-soluble acenothiadiazole-based bistriazoles with red-shifted absorption and emission characteristics.

Acidochromicity of bisarylethynylbenzenes: hydroxy versus dialkylamino substituents.

This contribution investigates the electronic difference of dibutylamino/dibutylammonium and phenol/phenolate groups in four simple distyrylbenzenes and bisarylethynylbenzenes. The compounds and their protonated and deprotonated species, respectively, were investigated by UV-vis and emission spectroscopies. While the anilinium and phenol compounds displayed similar spectroscopic properties, this was less so the case for the comparison of the dialkylanilines with the corresponding phenolates. In this case, the hydrogen bonding ability of the phenolates distorted the results as the hydrogen donating/accepting properties of the investigated solvents have a disproportional influence on the electronic properties of the phenolates when compared to the dialkylamines. If one uses acetonitrile as solvent, these effects disappear, as acetonitrile is neither a good hydrogen bond acceptor nor a hydrogen bond donor. The results are in line with the para-Hammet constant for OH (sigma = -0.37) being significantly smaller than that for NMe(2) substituents (sigma = -0.83) and reinforces the notion that the lone pairs in these phenols are not readily available for interaction with the pi-system, as they are perhaps energetically too low lying. However, in the case of the phenolates, the lone pairs do interact significantly.

Alkynylated aceno[2,1,3]thiadiazoles.

Enlarged acenothiadiazoles, which are easily prepared, display attractive optical and electrochemical properties. The annulation of thiadiazole to anthracene gives a stable material with optical properties similar to those of substituted pentacenes.

Are N,N-dihydrodiazatetracene derivatives antiaromatic?

The synthesis and X-ray characterization of two new dialkynylated diazatetracenes and the corresponding N, N-dihydrodiazatetracenes are reported. The dialkynylated heteroacenes are packed in a brick-wall motif that enforces significant overlap of their pi-faces. Cyclic voltammetry indicates that the dehydrogenated forms are easily reduced to their radical anions in solution. The planarity of these species validates the discussion of their aromaticity. Nucleus Independent Chemical Shift (NICS) computations demonstrate that both of these 20 pi and 24 pi electron systems are aromatic. Both experimental and computational results suggest that the aromaticity of the dihydroheteroacenes is reduced.

Terpyridine-based cruciform-Zn2+ complexes as anion-responsive fluorophores.

The synthesis of a terpyridine-appended, zinc-complexed cruciform, 3-Zn2+, and the anion-reactive modulation of its emissive properties in acetone-water mixtures are reported.

Hydroxy-cruciforms.

The synthesis of hydroxy-cruciforms 7 and 8 and their dramatically varying photophysical properties upon exposure to amines are reported.

A high-yield, one-step synthesis of o-phenylene ethynylene cyclic trimer via precipitation-driven alkyne metathesis.

[reaction: see text] A shape-persistent, conjugated o-phenylene ethynylene cyclic trimer was prepared in one step from tetrasubstituted benzene monomer 4 in 86% isolated yield through precipitation-driven alkyne metathesis. The template-free, selective generation of the molecular triangle 5 is a thermodynamically favored process and under equilibrium control. A novel tetrameric macrocycle 7 was generated via scrambling metathesis between tricycle 5 and hexacycle 6 using this dynamic covalent chemistry.