Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

The calculation of frequency-dependent hyperpolarizabilities including electron correlation effects

The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation.     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Enantio- and Diastereoselective Aldol-Reaction of 2,6-Dimethylphenyl Propionate Using Titanium-Carbohydrate Complexes

Chloro(cyclopentadienyl)bis(1,2:5,6-di-O-isopropylidene-α-D -glucofuranos-3-O-yl)titanium ( 1 ) is used for the transmetallation of Li-enolates obtained from propionyl derivatives. While such Ti-enolates of ketones and hydrazones appear to be unreactive, the (E)enolate 13 of 2,6-dimethylphenyl propionate ( 11 ) adds to the re-side of aldehydes, affording various syn-aldols 14 with high dia- and enantioselectivity (92–97% ds, 91–97% ee, cf. Scheme 2 and Table 1). Racemic syn-aldols (±)- 14 are obtained analogously from the achiral bis(2-propyloxy)-Ti-enolate 15 (Scheme 2 and Table 2). In contrast to the unstable Li-enolate 10 , the Ti-enolates 13 and 15 isomerize at ?30°, presumably to the thermodynamically more stable (Z)-enolates (Scheme 4), While the diastereoselectivity of the achiral enolate 15 is lost upon this equilibration, the chiral (Z)-enolate 27 quite unexpectedly affords anti-aldols 12 of high optical purity (94–98% ec) and, in most cases, with acceptable-to-good diastereoselectivity (82–90% ds). Notable exceptions are branched unsaturated and aromatic aldehydes which form a greater proportion of synepimers of moderate optical purity (Scheme 5 and Table 3). Consistent with these findings, re-facial-and ami -selective aldol-addition is also exhibited by the (Z)-configurated Ti-enolate 22 of N-propionyl-oxazolidi-none 19 (Scheme 3).     

Benzo[d]-1,2-oxaphospholes as precursors of stabilized C-centered radicals

[reaction: see text] Several benzo[d]-1,2-oxaphosphole 2-oxides were examined as potential precursors of stabilized C-centered radicals. The transient absorption spectra obtained after laser flash photolysis in the presence of di-tert-butyl peroxide showed the features of benzylic radicals with formation and decay kinetics not significantly influenced by the presence of oxygen. In the case of compounds with two possible diastereomeric forms, the C-H bond of the trans-isomers [corrected] is more reactive toward hydrogen abstraction.