First observation in the gas phase of the ultrafast electronic relaxation pathways of the S(2) states of heme and hemin

The time evolution of electronically excited heme (iron II protoporphyrin IX, [Fe(II) PP]) and its associated salt hemin (iron III protoporphyrin IX chloride, [Fe(III) PP-Cl]), has been investigated for the first time in the gas phase by femtosecond pump-probe spectroscopy. The porphyrins were excited at 400 nm in the S(2) state (Soret band) and their relaxation dynamics was probed by multiphoton ionization at 800 nm. This time evolution was compared with that of the excited state of zinc protoporphyrin IX [Zn PP] whose S(2) excited state likely decays to the long lived S(1) state through a conical intersection, in less than 100 fs. Instead, for [Fe(II) PP] and [Fe(III) PP-Cl], the key relaxation step from S(2) is interpreted as an ultrafast charge transfer from the porphyrin excited orbital π* to a vacant d orbital on the iron atom (ligand to metal charge transfer, LMCT). This intermediate LMCT state then relaxes to the ground state within 250 fs. Through this work a new, serendipitous, preparation step was found for Fe(II) porphyrins, in the gas phase.     

Polarization imaging of multiply-scattered radiation based on integral-vector Monte Carlo method

A new integral-vector Monte Carlo method (IVMCM) is developed to analyze the transfer of polarized radiation in 3D multiple scattering particle-laden media. The method is based on a “successive order of scattering series” expression of the integral formulation of the vector radiative transfer equation (VRTE) for application of efficient statistical tools to improve convergence of Monte Carlo calculations of integrals. After validation against reference results in plane-parallel layer backscattering configurations, the model is applied to a cubic container filled with uniformly distributed monodispersed particles and irradiated by a monochromatic narrow collimated beam. 2D lateral images of effective Mueller matrix elements are calculated in the case of spherical and fractal aggregate particles. Detailed analysis of multiple scattering regimes, which are very similar for unpolarized radiation transfer, allows identifying the sensitivity of polarization imaging to size and morphology.     

Non‐Blinking Semiconductor Colloidal Quantum Dots for Biology,Optoelectronics and Quantum Optics

Twinkle, twinkle: The blinking of semiconductor colloidal nanocrystals is the main inconvenience of these bright nanoemitters. There are various approaches for obtaining non‐blinking nanocrystals, one of which is to grow a thick coat of CdS on the CdSe core (see picture). Applications of this method in the fields of optoelectronic devices, biologic labelling and quantum information processing are discussed.

     

On a Theorem of Bandt and Wang and Its Extension to <Emphasis Type="Italic">p</Emphasis>2-tiles

We study tilings of the plane by a single prototile with respect to the lattice and to the crystallographic group p2. We are interested in the connection between the neighbors of a tile in the tiling and its topology. We show that lattice and p2-tiles always have at least six neighbors. We characterize self-affine tiles that are homeomorphic to a disk in a rather easy way by the set and number of neighbors of the central tile in the tiling. This extends the work of Bandt and Wang devoted to lattice self-affine disk-like tiles of the plane.     

Size and charge effects on the binding of CO to late transition metal clusters

We report on the size and charge dependence of the C-O stretching frequency, nu(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (Co(n)CO(-0+)), anionic, neutral, and cationic rhodium clusters (Rh(n)CO(-0+)), and cationic nickel clusters (Ni(n)CO(+)) for n up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to nu(CO) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO pi* orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as n increases. At large n, nu(CO) approaches asymptotes that are not the same as found for nu(CO) on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.     

Small molecule chemisorption on indium-tin oxide surfaces: enhancing probe molecule electron-transfer rates and the performance of organic light-emitting diodes

Indium-tin oxide (ITO) surfaces have been modified by chemisorption of carboxylic acid functionalized small molecules: ferrocene dicarboxylic acid (1), 3-thiophene acetic acid (2), and 6-{4-[{4'-[[4-(5-carboxy-pentyloxy)-phenyl]-(4-methoxy-phenyl)-amino]-biphenyl-4-yl}-(4-methoxy-phenyl)-amino]-phenoxy}-hexanoic acid (p-OMe)2-TPD-(C5-COOH)2) (3). Voltammetrically determined surface coverages of 1-3 increased in two stages, the first stage completing in minutes, the latter stage taking several hours. Electron-transfer rate coefficients, kS, for the probe molecule ferrocene in acetonitrile likewise increased in two stages with increasing surface coverages of 1, 2, and 3. Fourier transform infrared spectroscopy of In2O3 powders, exposed for long periods to ethanol solutions of each modifier, confirmed the formation of indium oxalate-like surface species. X-ray photoelectron spectroscopy of carboxy-terminated alkanethiol-modified gold surfaces, exposed to these same In2O3(powder)/small molecule modifier solutions, showed the capture of trace levels of indium as a result of the chemisorption of these small molecules, suggesting that slow etching of the ITO surface also occurs during the chemisorption event. Conventional aluminum quinolate/bis-triarylamine organic light-emitting diodes (OLEDs) created on ITO surfaces modified with 1, 2, and 3, with and without an overlayer of PEDOT:PSS (a poly(thiophene)/poly(stryenesulfonate) ITO modifier), showed leakage currents lowered by several orders of magnitude and an increase in OLED device efficiency.     

Rhodium-catalyzed carbometalation of ynamides with organoboron reagents

In the presence of catalytic [Rh(cod)(MeCN)₂]BF₄, ynamides undergo carbometalation with boronic acids, arylboronic esters, and triarylboroxines. These reactions enable the regio- and stereocontrolled synthesis of multisubstituted enamides.     

High-speed planar thermometry and velocimetry using thermographic phosphor particles

Simultaneous gas-phase temperature and velocity imaging using micrometer-size thermographic phosphor particles seeded into the flow is demonstrated at a 3 kHz repetition rate. The velocity field is measured using a standard particle image velocimetry approach, while the temperature is determined from the temperature sensitive phosphorescence emission of the particles following excitation at 355 nm. Since the particles are very small, they rapidly assume the temperature and velocity of the surrounding gas. A single shot temperature precision of better than 5 % was achieved at 500 K. Time-resolved measurements in the wake of a heated cylinder are presented, demonstrating the utility of these imaging diagnostics to observe transient, coupled heat and mass transfer phenomena.     

Bis((2-methoxymethyl)pyrrolidine)phosphine as effective chiral auxiliary for the stereoselective synthesis of chiral ferrocenyl diphosphines

The bis(2-methoxymethyl pyrrolidine)phosphine moiety is shown to be a very effective chiral auxiliary for the ortho- and diastereoselective lithiation of ferrocene, thereby allowing the highly selective attachment of various electrophiles to the cyclopentadienyl ring of ferrocene. The potential of the methodology is demonstrated by the synthesis of Kephos, a new family of ferrocenyl diphosphines and of OH-Taniaphos derivatives.