ChemPhysChem

Cover image for Vol. 10 Issue 12

August 24, 2009

Volume 10, Issue 12

Pages 1941–2155

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. Cover Picture: Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering) (ChemPhysChem 12/2009) (page 1941)

      Tae Kyu Kim, Jae Hyuk Lee, Michael Wulff, Qingyu Kong and Hyotcherl Ihee

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200990044

      Thumbnail image of graphical abstract

      The cover picture illustrates the technique of time-resolved X-ray liquidography (solution scattering), a direct tool to probe structural dynamics and spatiotemporal kinetics of solution-phase reactions. Picosecond optical pulses (red line) trigger a chemical reaction in a solution and 100 ps long X-ray pulses (cyan line) from a synchrotron probe the evolving structures of transient species over picoseconds to microseconds. Molecules ranging from small molecules to organometallic complexes, nanoparticles and proteins are studied. In the corners are shown time-dependent difference scattering patterns for the iodine elimination reaction of 1,2-diiodoethane (C2H4I2) in a methanol solution, along with the associated major transient structures identified via data analysis. On page 1958 H. Ihee et al. review experimental and theoretical approaches, application examples and future perspectives for femtosecond applications of this technique.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. Reversible Molecular Logic: A Photophysical Example of a Feynman Gate (page 1942)

      Patricia Remón, Rita Ferreira, Jose-Maria Montenegro, Rafael Suau, Ezequiel Pérez-Inestrosa and Uwe Pischel

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200990045

      Thumbnail image of graphical abstract

      Reversible molecular logic with a cocktail of two parallel operating fluorophores is shown. Combinations of two chemical inputs induce four different fluorescence outputs as seen in the photograph. This corresponds to one-to-one mapping of input and output vectors, implemented by a Feynman logic gate, as described by E. Pérez-Inestrosa, U. Pischel et al on p. 2004.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
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    1. Graphical Abstract: ChemPhysChem 12/2009 (pages 1943–1952)

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200990046

  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. You have free access to this content
      Carbon-Centered Radical Addition and β-Scission Reactions: Modeling of Activation Energies and Pre-exponential Factors (page 1951)

      Maarten K. Sabbe, Marie-Françoise Reyniers, Veronique Van Speybroeck, Michel Waroquier and Guy B. Marin

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200990047

      This article corrects:
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
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  6. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
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    1. Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering) (pages 1958–1980)

      Tae Kyu Kim, Jae Hyuk Lee, Michael Wulff, Qingyu Kong and Hyotcherl Ihee

      Article first published online: 7 JUL 2009 | DOI: 10.1002/cphc.200900154

      Thumbnail image of graphical abstract

      Time and motion: Time-resolved X-ray liquidography (see picture) can directly probe the structural dynamics and spatiotemporal kinetics of the liquid phase with unprecedented spatial and temporal resolution. Recent developments in this method, including technical innovations, theoretical analysis, and several examples ranging from simple molecules to protein solutions, are reviewed.

      Corrected by:

      Corrigendum: Corrigendum: Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering)

      Vol. 11, Issue 14, 3034, Article first published online: 24 SEP 2010

      Corrected by:

      Corrigendum: Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering)

      Vol. 10, Issue 17, 2915, Article first published online: 30 NOV 2009

      Corrected by:

      Corrigendum: Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering)

      Vol. 10, Issue 18, 3140, Article first published online: 10 DEC 2009

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. Jiggling of Coherent Excitons along a Polymer Chain (pages 1981–1982)

      Kankan Bhattacharyya

      Article first published online: 27 JUN 2009 | DOI: 10.1002/cphc.200900202

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      Exciton migration: Intra-molecular electronic energy transfer, EET (scheme a), in a conjugated polymer (extended MEH-PPV in a good solvent) exhibits coherence in 200 fs. For inter-molecular EET (scheme b, in collapsed MEH-PPV nanoparticle), uncorrelated fluctuations lead to rapid de-coherence (<10 fs).

    2. Cross-Polarization Detection Enables Fast Measurement of Vibrational Circular Dichroism (pages 1983–1985)

      Petr Bouř

      Article first published online: 9 JUN 2009 | DOI: 10.1002/cphc.200900383

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      Vibrational circular dichroism: Normally, a femtosecond pulse would be too short to produce a spectrum. This may be possible with the heterodyned Fourier transform spectral interferometry and a pump–probe pulse scheme. The new technique already provided spectra of limonene (see picture), so far without time resolution.

  8. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
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    1. Dissecting the Hindered Rotation of Ethane (pages 1987–1992)

      David Asturiol, Pedro Salvador and István Mayer

      Article first published online: 22 MAY 2009 | DOI: 10.1002/cphc.200900089

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      With a twist: The rotational barrier of ethane (see picture) is analyzed in terms of atomic and diatomic contributions of the energy. No charge-localized reference state is necessary. Hyperconjugation effects give rise to different individual energy components that cancel almost completely. The picture of attributing the barrier to the repulsion between the hydrogen atoms is legitimate.

    2. Phototriggered Metal-Ion Release from Phenolic Schiff Bases: A System for Metal-Ion Photodelivery (pages 1993–1995)

      Xu Zhang and Yi Chen

      Article first published online: 9 JUN 2009 | DOI: 10.1002/cphc.200900070

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      A phototriggered system for metal-ion release is developed using a phenolic Schiff-base derivative as ligand (see scheme). It is found that Zn2+ can be completely released from the ligand by using a phototrigger. The metal-releasing system is also active for other bivalent metal ions.

    3. Electrical Switching of 1,2-Bis(2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene in the Solid State (pages 1996–1999)

      Hui Lin, Zhongming Wei, Junfeng Xiang, Wei Xu and Daoben Zhu

      Article first published online: 11 JUL 2009 | DOI: 10.1002/cphc.200900232

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      Photochromic reactions occurring in the solid state are studied by using solid-state 13C NMR and IR spectroscopy. Electrical switching of small-molecule photochromic compounds is observed on single crystals and thin films. The figure shows the voltage–current characteristics of a thin film of a dithienylethene derivative before (○) and after (•) UV irradiation.

    4. Photothermally Induced Microchemical Functionalization of Organic Monolayers (pages 2000–2003)

      Benjamin Klingebiel, Anja Schröter, Steffen Franzka and Nils Hartmann

      Article first published online: 26 MAY 2009 | DOI: 10.1002/cphc.200900278

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      A prototype photothermal procedure: Alkylsiloxane monolayers on surface-oxidized silicon substrates are processed in gaseous bromine using a focused Ar+-laser operated at λ=514 nm. Monolayer bromination remains confined to a micrometer-sized reaction zone, where laser irradiation results in a local temperature rise (see figure).

    5. Reversible Molecular Logic: A Photophysical Example of a Feynman Gate (pages 2004–2007)

      Patricia Remón, Rita Ferreira, Jose-Maria Montenegro, Rafael Suau, Ezequiel Pérez-Inestrosa and Uwe Pischel

      Article first published online: 24 JUN 2009 | DOI: 10.1002/cphc.200900375

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      Return trip included! The first molecular realization of a reversible logic operation with a simple cocktail of two classical fluorophores is demonstrated (see figure). Protons and anions, which serve as inputs, trigger independent fluorescence answer signals. Thus, XOR and YES gates are straightforward implemented, resulting in reversible logic behavior.

    6. Steering Two-Dimensional Molecular Growth via Dipolar Interaction (pages 2008–2011)

      Stefan Kuck, Shih-Hsin Chang, Jan-Peter Klöckner, Marc Heinrich Prosenc, Germar Hoffmann and Roland Wiesendanger

      Article first published online: 30 JUN 2009 | DOI: 10.1002/cphc.200900281

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      Molecular networks: Chiral and metallized Salen molecules on a Cu(111) are investigated using local probe techniques (see figure). Whereas for the parent Co-Salen molecule no self-assembly is observed, in the metal–organic complexes the growth of large and regular molecular networks is achieved through a target-oriented synthetic design of the local electrostatic dipolar molecular fields.

    7. Blue Luminescence Emitted from Monodisperse Thiolate-Capped Au11 Clusters (pages 2012–2015)

      Zhijiang Wang, Wei Cai and Jiehe Sui

      Article first published online: 30 JUN 2009 | DOI: 10.1002/cphc.200900067

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      Blu-ray balls: Au11 clusters were synthesized in the presence of carboxylic-acid-terminated thiolated molecules. Due to the protection of the monodisperse clusters from quenchers in the solution by the high-density ligands, the Au11 clusters exhibit blue luminescence with a QY of 8.6 % (see picture). They have great potential for applications of novel fluorophores.

  9. Articles

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. A Vibrational Raman Optical Activity Study of 1,1′-Binaphthyl Derivatives (pages 2017–2025)

      Vincent Liégeois

      Article first published online: 3 JUL 2009 | DOI: 10.1002/cphc.200900115

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      Key signatures: Vibrational Raman optical activity (VROA) backward spectra are simulated for the 1,1′-binaphthyl compound in its cisoid (left in figure) and transoid (right) conformations. Both conformations have distinct VROA patterns, as illustrated by their atomic contributions to the VROA intensity for the mode at 1350 cm−1 represented by a red impulse.

    2. Internal Architecture and Adsorption Sites of Violet Lander Molecules Assembled on Native and KBr-Passivated InSb(001) Surfaces (pages 2026–2033)

      Szymon Godlewski, Grzegorz Goryl, Andre Gourdon, Jacek J. Kolodziej, Bartosz Such and Marek Szymonski

      Article first published online: 26 MAY 2009 | DOI: 10.1002/cphc.200900128

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      The color purple: Low-temperature scanning tunneling microscopy is applied to investigate the adsorption and self-assembly of Violet Lander molecules on native and KBr-passivated InSb c(8×2) reconstructed surfaces (see picture). Several different molecular conformations, adjusted to the anisotropic structure of the substrate, are observed. Tip-induced lateral manipulation of large molecules with spacer groups is proved to be feasible and controllable.

    3. Effect of the Constrained Environment on the Interactions between the Surfactant and Different Polar Solvents Encapsulated within AOT Reverse Micelles (pages 2034–2040)

      Andrés M. Durantini, R. Dario Falcone, Juana J. Silber and N. Mariano Correa

      Article first published online: 26 MAY 2009 | DOI: 10.1002/cphc.200900130

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      Interesting interactions: FTIR spectroscopy is applied to study the interactions between different nonaqueous polar solvents and sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) in nonaqueous AOT/n-heptane reverse micelles. The figure shows a schematic representation of various micelle interfaces obtained with different polar solvents (GY=glycerol; EG=ethylene glycol; DMF=dimethylformamide).

    4. Fluorophores as Optical Sensors for Local Forces (pages 2041–2048)

      Stefan Marawske, Denis Dörr, Daniel Schmitz, Axel Koslowski, You Lu, Helmut Ritter, Walter Thiel, Claus A. M. Seidel and Ralf Kühnemuth

      Article first published online: 26 MAY 2009 | DOI: 10.1002/cphc.200900240

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      Optical force sensor: To explore the use of fluorophores as optical sensors for local mechanical forces, a custom-tailored chromophore is synthesized and aligned in a flexible polyvinyl chloride matrix by stretching (see picture). Applying tensile stress causes a decrease in the fluorescence lifetime by 2.5 % and a blue-shift of the fluorescence spectrum of 1.2 nm, consistent with the predictions from semiempirical calculations.

    5. Intensity-Carrying Modes in Raman and Raman Optical Activity Spectroscopy (pages 2049–2057)

      Sandra Luber and Markus Reiher

      Article first published online: 6 JUL 2009 | DOI: 10.1002/cphc.200900255

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      A quantum-chemical approach for the determination of modes with maximum Raman and Raman optical activity (ROA) intensity is presented. The intensity-carrying modes are hypothetical modes that provide information about those molecular distortions leading to intense bands in the spectrum. Modes with maximum Raman optical activity intensity are presented for Λ-tris(propane-1,3-dionato)cobalt(III) [see picture].

    6. Stabilization and Large Nonlinearity of Gold Nanoparticles Functionalized with a π-Conjugated Polymer (pages 2058–2065)

      Cuihong Li, Li Jiang, Huibiao Liu, Yuliang Li and Yinglin Song

      Article first published online: 30 JUL 2009 | DOI: 10.1002/cphc.200900015

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      Stable mates: Gold nanoparticles protected by a novel π-conjugated polymer show an exceptional nonlinear absorption effect (see picture), which simultaneously contains saturated absorption resulting from third-order nonlinearity and large reverse-saturated absorption resulting from fifth-order nonlinearity.

    7. Fluorescent Alteration on a Bistable Molecular Shuttle (pages 2066–2072)

      Weidong Zhou, Shuai Zhang, Guoxing Li, Yingjie Zhao, Zhiqiang Shi, Huibiao Liu and Yuliang Li

      Article first published online: 16 JUL 2009 | DOI: 10.1002/cphc.200900228

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      Artificial motors: Solvent-driven molecular shuttles containing a pyrene-connected macrocycle and an intramolecular charge-transfer (ICT) chromophore stopper (TDPD) are constructed. The macrocycle is located close to or far from the chromophore in apolar and polar solvents, respectively, which alters the fluorescent emission of the pyrene probe in the macrocycle (see figure).

    8. Excited State Intramolecular Proton Transfer and Photophysics of a New Fluorenyl Two-Photon Fluorescent Probe (pages 2073–2081)

      Alma R. Morales, Katherine J. Schafer-Hales, Ciceron O. Yanez, Mykhailo V. Bondar, Olga V. Przhonska, Adam I. Marcus and Kevin D. Belfield

      Article first published online: 15 MAY 2009 | DOI: 10.1002/cphc.200900032

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      New two-photon fluorescent probe: Comprehensive photophysical and two-photon absorption properties of a new fluorene derivative containing the 2-(2′-hydroxyphenyl)benzothiazole terminal construct are investigated (see figure). The potential use of this fluorenyl probe in bioimaging is demonstrated via one- and two-photon fluorescence imaging of COS-7 cells.

    9. Direct Volumetric Measurement of Gas Oversolubility in Nanoliquids: Beyond Henry’s Law (pages 2082–2089)

      Marc Pera-Titus, Rayan El-Chahal, Volainiana Rakotovao, Cécile Daniel, Sylvain Miachon and Jean-Alain Dalmon

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200900058

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      Enhanced gas solubility in nanoliquids, that is, in solvents confined in mesopores of solids, is directly measured by volumetry for H2 in five solvents. Gas solubilities in liquids are enhanced up to 15-fold over the corresponding bulk values for nanoliquid sizes smaller than 15 nm (see bar chart). Previous observations by 1H NMR spectroscopy are confirmed, and the role of surface excess concentrations at mesoconfined gas/liquid interfaces in enhancing the gas solubility is discussed.

    10. X-ray Absorption Spectroscopy as a Probe of Photo- and Thermally Induced Valence Tautomeric Transition in a 1:1 Cobalt–Dioxolene Complex (pages 2090–2095)

      Giordano Poneti, Matteo Mannini, Lorenzo Sorace, Philippe Sainctavit, Marie-Anne Arrio, Andrei Rogalev, Fabrice Wilhelm and Andrea Dei

      Article first published online: 5 JUN 2009 | DOI: 10.1002/cphc.200900098

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      Probing bistable systems: X-ray absorption near-edge spectroscopy (XANES) is successfully applied to probe the thermally and light-induced valence tautomeric interconversion in a 1:1 Co–dioxolene complex (see picture).

    11. Exciton Diffusion in Polyfluorene Copolymer Thin Films: Kinetics, Energy Disorder and Thermally Assisted Hopping (pages 2096–2104)

      Fernando B. Dias, Kiran T. Kamtekar, Thiago Cazati, Geoff Williams, Martin R. Bryce and Andrew P. Monkman

      Article first published online: 15 MAY 2009 | DOI: 10.1002/cphc.200900112

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      Thermally versus non-thermally assisted exciton migration: The population of the excited state of a “red” emitting trap is controlled by exciton migration in the copolymer host, showing an energy barrier of 20 meV that turns over to a non-activated regime below 200 K (see figure).

    12. C[BOND]X⋅⋅⋅O Halogen Bonding: Interactions of Trifluoromethyl Halides with Dimethyl Ether (pages 2105–2115)

      Dieter Hauchecorne, Roman Szostak, Wouter A. Herrebout and Benjamin J. van der Veken

      Article first published online: 3 JUL 2009 | DOI: 10.1002/cphc.200900125

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      The other non-bonding interaction: Raman and infrared spectra of solutions in cryogenic solvents reveal the formation of halogen-bonded complexes of trifluoromethyl chloride, bromide and iodide with dimethylether (see picture), with strengths varying between 7 and 15 kJ mol−1.

    13. Geometric Model Describing the Banded Morphology of Particle Films Formed by Convective Assembly (pages 2116–2122)

      J. Alex Lee, Kayla Reibel, Mark A. Snyder, L. E. Scriven and Michael Tsapatsis

      Article first published online: 3 JUL 2009 | DOI: 10.1002/cphc.200900127

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      Banded particle films: Convective assembly of particles from dilute suspensions can produce discrete film morphologies in the form of bands. The spacing between such bands, when they are in a monolayer, is a strong function of the particle size. A geometric model considering the intersection of the particles with a stretched liquid meniscus can quantitatively predict these spacings with varying particle diameter (see picture).

    14. Frank Model and Spontaneous Emergence of Chirality in Closed Systems (pages 2123–2131)

      Joaquim Crusats, David Hochberg, Albert Moyano and Josep M. Ribó

      Article first published online: 5 JUN 2009 | DOI: 10.1002/cphc.200900181

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      Unbalanced: An enantioselective autocatalytic reaction coupled to the exergonic and fast formation of the heterochiral dimer may lead to a kinetically controlled spontaneous mirror symmetry breaking. The key feature is the non-linear effect arising from the mutual inhibition step (heterochiral dimerization) coupled to the enantioselective autocatalysis (see graph).

    15. Theoretical Simulation of Vibrational Sum-Frequency Generation Spectra from Density Functional Theory: Application to p-Nitrothiophenol and 2,4-Dinitroaniline (pages 2132–2142)

      Julien Guthmuller, Francesca Cecchet, Dan Lis, Yves Caudano, Alaa Addin Mani, Paul A. Thiry, André Peremans and Benoît Champagne

      Article first published online: 9 JUN 2009 | DOI: 10.1002/cphc.200900184

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      Summing up: A theoretical methodology simulates vibrational sum-frequency generation (SFG) spectra for different combinations of polarizations and is applied to p-nitrothiophenol and 2,4-dinitroaniline. The IR vectors and Raman tensors are calculated with DFT. Comparison of such simulations with experiment allows determination of the molecular orientation (see picture).

    16. The Role of Triphenylamine in the Stabilization of Highly Efficient Polyfluorene-Based OLEDs: A Model Oligomers Study (pages 2143–2149)

      Mariacecilia Pasini, Umberto Giovanella, Paolo Betti, Alberto Bolognesi, Chiara Botta, Silvia Destri, William Porzio, Barbara Vercelli and Gianni Zotti

      Article first published online: 19 JUN 2009 | DOI: 10.1002/cphc.200900260

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      Highly stable and efficient polyfluorene: Triphenylamine (TPA) introduced as a lateral fluorene substituent of polyfluorene (PFO) prevents keto-defect formation, which leads to improved performances and colour stability of devices. Ad hoc synthesized model oligomers are used to monitor energy transfer between fluorene and fluorenone moieties (see figure).

  10. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Preview
    1. Preview: ChemPhysChem 13/2009 (page 2155)

      Article first published online: 18 AUG 2009 | DOI: 10.1002/cphc.200990049

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