Real-time charge oscillation between monomers in a dimeric system associated with intermolecular vibration induced by an ultrashort pulse

Ultrafast charge resonant (CR) dynamics between two molecules in a dimer system has been studied theoretically and experimentally using 6-fs laser pulses and a thin film of amorphous-phase phthalocyanine tin(IV) dichloride (SnPc). The modulation of the absorbance change in the bleaching spectral range of the CR absorption band was analyzed to obtain the amount of charge resonantly transferred back and forth by a dimeric vibration induced by photoexcitation. The modulation can be explained in terms of a periodic change in the cross section and a periodic energy shift, where both are induced by the change in the overlap integral caused by the accordion-type intermolecular vibration. The associated change in distance between two molecules with the intermolecular vibration was estimated to be 0.09 A, which corresponds to 2.5% of the mean distance between the two SnPc molecules in the dimeric system.     

Carrier-envelope phase-controlled quantum interference in optical poling

We demonstrate the efficiency of the optical poling process that depends on the CE phase-controlled quantum interference. For the experiment we employed our noncollinear optical parametric amplifier system for the self-stabilization of the CE phase, with the f-to-2f spectral interferometry system to control the CE phase.     

Reactive barium-promoted Reformatsky-type reaction of alpha-chloroketones with aldehydes

A Reformatsky-type aldol reaction of alpha-chloroketones with aldehydes has been achieved using reactive barium as a low-valent metal in THF; this one-pot process is more effective for obtaining the desired beta-hydroxy ketones in high yields than the stepwise process in which barium enolates are prepared prior to the reaction with aldehydes.     

Iridium complex-catalyzed highly enantio- and diastereoselective [2+2+2] cycloaddition for the synthesis of axially chiral teraryl compounds

An asymmetric [2+2+2] cycloaddition of an alpha,omega-diyne, possessing ortho-substituted aryl groups on its terminus, and a monoalkyne with oxygen functionalities gave various axially chiral teraryl compounds. The coupling proceeded with extremely high enantio- (>99.5% ee) and diastereoselectivities (dl/meso = >95/5) when catalyzed by an iridium-chiral phosphine complex. As the products were readily transformed into diol compounds by deprotection without racemization, the present procedure provides access to a new chiral pool of diol compounds with C2 symmetry.     

Electronic properties of CrF and CrCl in the X 6Sigma+ state: observation of the halogen hyperfine structure by Fourier transform microwave spectroscopy

The rotational spectra of the CrF and CrCl radicals in the X 6Sigma+ state were observed by employing a Fourier transform microwave spectrometer. The CrF and CrCl radicals were generated by the reaction of laser-ablated Cr with F2 and Cl2, respectively, diluted in Ar. A chromium rod made of chromium powder pasted with epoxy resin was ablated by a Nd:YAG laser. Rotational transitions were measured in the region between 8 and 26 GHz. Several hyperfine constants due to the halogen nuclei were determined by a least-squares analysis. The electronic properties of CrF and CrCl were derived from their hyperfine constants and were compared with those of other 3d transition metal monohalides: TiF, MnF, FeF, CoF, NiF, and FeCl.     

Simultaneous observation of low temperature 4f-4f and 3d-3d emission spectra in a series of Cr(III)(ox)Ln(III) assembly

We report here the low temperature emission spectra in the heterometal dinuclear 3d-4f assembled molecular system [(acac)₂Cr^III(μ-ox)Ln^III(HBpz₃)₂] (Cr(ox)Ln:acac⁻=acetylacetonate, ox²⁻=oxalate, HBpz₃⁻=hydrotris(pyrazol-1-yl)borate; Ln=La, Nd, Ho, Er , Tm and Yb) in comparison with those of Na[Cr(acac)₂(ox)] and [(HBpz₃)₂Ln(μ-ox)Ln(HBpz₃)₂](Ln=Nd and Er). From 10 to 150 K the Cr(ox)Ln complexes show a broad emission band around 800 nm from the ²E state of Cr(III) moiety. At room temperature no ²E-⁴A₂ emission was observed in the Cr(ox)Ln except for the La and Lu complexes. On warming from 10 to 300 K rapid quenching of the ²E-⁴A₂ emission of Cr(III) is suggested to result from the energy transfer from Cr to Ln in the Cr(ox)Ln. The excitation spectra and the life-time were also measured with monitoring the 4f-4f emission peaks of the Cr(ox)Yb complex.     

Long-lived charge-separated state leading to DNA damage through hole transfer

The hole transfer causes the long-lived charge-separated state in DNA during the photosensitized one-electron oxidation of DNA. The combination of the transient absorption measurement and DNA damage quantification by HPLC clearly demonstrated that the yield of the DNA damage correlates well with the lifetime of the charge-separated state.     

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

The Pt-catalyzed carboselenation of alkynes by selenoesters

[reaction: see text] The Pt-catalyzed carboselenation of terminal alkynes with selenoesters provided vinylselenides regio- and stereoselectively in moderate yields.