Scalable synthesis of functionalised 2-pyridones via [4+2] cycloaddition reactions of 2-pyrazinones and alkynylboronates

The multigram synthesis of N-protected 2-pyridone boronic acid derivatives via a [4+2] cycloaddition of alkynylboronates with 2-pyrazinones is presented. The reactions are highly chemoselective, and generally highly regioselective although trimethylsilyl-substituted alkynylboronates have proven to be an exception. Nonetheless, in this latter case, separation of regioisomers was successfully accomplished via high performance counter-current chromatography allowing isolation of analytically pure 2-pyridones. Further derivatisations of trimethylsilyl-substituted 2-pyridone boronates were performed providing access to a selection of functionalised scaffolds.     

Studies of the optogalvanic effect in a commercial caesium hollow cathode lamp and its use for tuning pulsed dye lasers

The use of the optogalvanic effect (OGE) in a hollow cathode lamp for wavelength tuning of dye lasers is an established technique at laser wavelengths longer than 560 nm, corresponding to photon energies less than 2.2 eV. This work describes the first successful optogalvanic studies on caesium at higher photon energies. Once set up, OGE in a standard commercial hollow cathode lamp provides a quick and cheap means of tuning a continuously tunable laser to a chosen atomic transition. The lines in caesium at 455.55 nm and 459.32 nm were resolved. This work is also believed to be the first to describe the detection of any caesium transition using the optogalvanic effect in a commercial hollow cathode lamp, rather than a specially constructed tube. The method used is applicable to other materials which have previously proved difficult.     

Magnetic-field-induced lattice anomaly inside the superconducting state of CeCoIn5: anisotropic evidence of the possible Fulde-Ferrell-Larkin-Ovchinnikov state

We report high magnetic field linear magnetostriction experiments on CeCoIn5 single crystals. Two features are remarkable: (i) a sharp discontinuity in all the crystallographic axes associated with the upper superconducting critical field B(c2) that becomes less pronounced as the temperature increases and (ii) a distinctive second orderlike feature observed only along the c axis in the high field (10 T < or approximately B< or = B(c2)) low temperature (T < or approximately 0.35 K) region. This second order transition is observed only when the magnetic field lies within 20 degrees of the ab planes and there is no signature of it above B(c2), which raises questions regarding its interpretation as a field induced magnetically ordered phase. Good agreement with previous results suggests that this anomaly is related to the transition to a possible Fulde-Ferrel-Larkin-Ovchinnikov superconducting state.     

Persistence to high temperatures of interlayer coherence in an organic superconductor

The interlayer magnetoresistance rho(zz) of the organic metal kappa-(BEDT-TTF)(2)Cu(NCS)(2) is studied in fields of up to 45 T and at temperatures T from 0.5 to 30 K. The peak in rho(zz) seen in in-plane fields, a definitive signature of interlayer coherence, remains to Ts exceeding the Anderson criterion for incoherent transport by a factor approximately 30. Angle-dependent magnetoresistance oscillations are modeled using an approach based on field-induced quasiparticle paths on a 3D Fermi surface, to yield the T dependence of the scattering rate tau(-1). The results suggest that tau(-1) does not vary strongly over the Fermi surface, and that it has a T(2) dependence due to electron-electron scattering.     

Experimental and theoretical studies on organic D-π-A systems containing three-coordinate boron moieties as both π-donor and π-acceptor

Four linear π-conjugated systems with 1,3-diethyl-1,3,2-benzodiazaborolyl [C(6)H(4)(NEt)(2)B] as a π-donor at one end and dimesitylboryl (BMes(2)) as a π-acceptor at the other end were synthesized. These unusual push-pull systems contain phenylene (-1,4-C(6)H(4)-; 1), biphenylene (-4,4'-(1,1'-C(6)H(4))(2)-; 2), thiophene (-2,5-C(4)H(2)S-; 3), and dithiophene (-5,5'-(2,2'-C(4)H(2)S)(2)-; 4) as π-conjugated bridges and different types of three-coordinate boron moieties serving as both π-donor and π-acceptor. Molecular structures of 2, 3, and 4 were determined by single-crystal X-ray diffraction. Photophysical studies on these systems reveal blue-green fluorescence in all compounds. The Stokes shifts for 1, 2, and 3 are notably large at 7820-9760 cm(-1) in THF and 5430-6210 cm(-1) in cyclohexane, whereas the Stokes shift for 4 is significantly smaller at 5510 cm(-1) in THF and 2450 cm(-1) in cyclohexane. Calculations on model systems 1'-4' show the HOMO to be mainly diazaborolyl in character and the LUMO to be dominated by the empty p orbital at the boron atom of the BMes(2) group. However, there are considerable dithiophene bridge contributions to both orbitals in 4'. From the experimental data and MO calculations, the π-electron-donating strength of the 1,3-diethyl-1,3,2-benzodiazaborolyl group was found to lie between that of methoxy and dimethylamino groups. TD-DFT calculations on 1'-4', using B3LYP and CAM-B3LYP functionals, provide insight into the absorption and emission processes. B3LYP predicts that both the absorption and emission processes have strong charge-transfer character. CAM-B3LYP which, unlike B3LYP, contains the physics necessary to describe charge-transfer excitations, predicts only a limited amount of charge transfer upon absorption, but somewhat more upon emission. The excited-state (S(1)) geometries show the borolyl group to be significantly altered compared to the ground-state (S(0)) geometries. This borolyl group reorganization in the excited state is believed to be responsible for the large Stokes shifts in organic systems containing benzodiazaborolyl groups in these and related compounds.     

Verification of a model to predict the influence of particle inertia and gravity on a decaying turbulent particle-laden flow

In an earlier publication some of the authors presented a theoretical model for the calculation of the influence of particle inertia and gravity on the turbulence in a stationary particle-laden flow. In the present publication the model is extended for application to a decaying suspension. Also a comparison is given between predictions made with the model and experimental data (own data and data reported in the literature) on a decaying turbulent flow with particles in a water tunnel or in a wind tunnel. For most of the experiments a prediction with reasonable accuracy and an interpretation is possible by means of the model.