Intramolecular Ketone-Olefin Radical Cyclization with Low-Valent Titanium Reagent: Synthesis of Benzopyrans

A novel protocol for intramolecular ketyl-olefin radical cyclization with low-valent titanium reagent is outlined. It allows the formation of the benzopyran nucleus from ortho-allyloxy propiophenones as the sole product in moderate yields via intramolecular radical cyclization.     

Use of the Bell–Evans–Polanyi Principle to predict regioselectivity of nucleophilic aromatic photosubstitution reactions

Regioselectivity of nucleophilic aromatic photosubstitution has been shown experimentally to depend upon activation energies of the competing transition states. Computational means of determining relative activation energies were sought, therefore, in order to predict regioselectivity. Optimization of the three triplet transition states of 2-chloro-4-nitroanisole with hydroxide ion gave energies of insufficient accuracy to predict regioselectivity. Computed enthalpy changes from the first triplet transition state to the triplet σ-complexes correlated precisely with the experimental activation energies. This exemplifies the Bell–Evans–Polanyi Principle, and it provides an accurate means of assessing regioselectivity.     

Novel Red Phosphorescent Polymers Bearing Both Ambipolar and Functionalized IrIII Phosphorescent Moieties for Highly Efficient Organic Light‐Emitting Diodes

A series of novel red phosphorescent polymers is successfully developed through Suzuki cross‐coupling among ambipolar units, functionalized Ir^III phosphorescent blocks, and fluorene‐based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy‐transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light‐emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η _L) of 8.31 cd A⁻¹, external quantum efficiency (η _ext) of 16.07%, and power efficiency (η _P) of 2.95 lm W⁻¹, representing the state‐of‐the‐art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.

     

The Total Solubility of the Co-Solubilized PAHs with Similar Structures Indicated by NMR Chemical Shift

The synergism/inhibition level, solubilization sites and the total solubility (S_t) of co-solubilization systems of phenanthrene, anthracene and pyrene in Tween 80 and sodium dodecyl sulfate (SDS) are studied by ¹H-NMR, 2D nuclear overhauser effect spectroscopy (NOESY) and rotating frame overhauser effect spectroscopy (ROESY). In Tween 80, inhibition for phenanthrene, anthracene and pyrene is observed in most binary and ternary systems. However, in SDS, synergism is predominant. After analysis, we find that the different synergism or inhibition situation between Tween 80 and SDS is related to the different types of surfactants used and the resulting different co-solubilization mechanisms. In addition, we also find that three polycyclic aromatic hydrocarbons (PAHs) have similar solubilization sites in both Tween 80 and SDS, which are almost unchanged in co-solubilization systems. Due to the similar solubilization sites, the chemical shift changes of surfactant and PAH protons follow the same pattern in all solubilization systems, and the order of chemical shift changes is consistent with the order of changes in the St of PAHs. In this case, it is feasible to evaluate S_t of PAHs by chemical shift. In both Tween 80 and SDS solutions, the ternary solubilization system has relatively high S_t rankings. Therefore, in practical applications, a good overall solubilization effect can be expected.     

Synthesis and characterization of an unexpected mechanochromicbistricyclic aromatic ene

An unexpected bistricyclic aromatic ene AF was synthesized in a tin(II) chloride-mediated reductive aromatization reaction. The obtained AF showed a highly overcrowded structural conformation as revealed by X-ray crystallography. Interestingly, AF exhibited reversible high-contrast mechanochromism and thermochromism between pale and red color. The obvious chromism is likely ascribed to the conformation transformation and trace amount of diradical species formation upon stimulus.     

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

The solution‐phase synthesis is one of the most promising strategies for the preparation of well‐defined graphene nanoribbons (GNRs) in large scale. To prepare high quality, defect‐free GNRs, cycloaromatization reactions need to be very efficient, proceed without side reaction and mild enough to accommodate the presence of various functional groups. In this Minireview, we present the latest synthetic approaches for the synthesis of GNRs and related structures, including alkyne benzannulation, photochemical cyclodehydrohalogenation, Mallory and Pd‐ and Ni‐catalyzed reactions.     

The Molecular Composition of Soot

Soot (sometimes referred to as black carbon) is produced when hydrocarbon fuels are burned. Our hypothesis is that polynuclear aromatic hydrocarbon (PAH) molecules are the dominant component of soot, with individual PAH molecules forming ordered stacks that agglomerate into primary particles (PP). Here we show that the PAH composition of soot can be exactly determined and spatially resolved by low‐fluence laser desorption ionization, coupled with high‐resolution mass spectrometry imaging. This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. As informed by chemical graph theory (CGT), the vast majority of species observed in the sampled particulate matter may be described as benzenoids, consisting of only fused 6‐membered rings. Within that limit, there is clear evidence for the presence of radical PAH in the particulate samples. Further, for benzenoid structures the observed empirical formulae limit the observed isomers to those which are nearly circular with high aromatic conjugation lengths for a given aromatic ring count. These results stand in contrast to recent reports that suggest higher aliphatic composition of primary particles.     

Unsaturated polyamides and polyesters prepared from 1,4-bis(2-carboxyvinyl)benzene and 4-hydroxycinnamic acid

Various unsaturated polyamides and polyesters were prepared from the reactions of 1,4-bis(2-carboxyvinyl)benzene acid chloride with aromatic diamines and bisphenols, respectively. In addition, various unsaturated homo- and copolyesters were synthesized from 4-hydroxycinnamic acid and 4-hydroxybenzoic acid. They were heat-cured to thermally stable resins. The polymers were characterized by inherent viscosity measurements, FT-IR, x-ray, DTA, TMA, TGA, and isothermal gravimetric analysis. The water absorption as well as the solubility behavior of the polymers was also investigated. © 1996 John Wiley & Sons, Inc.     

Catalytic hydrogenation of aromatic nitro compounds by non-noble metal complexes of chitosan

Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.