Mark Van der Auweraer

Temperature-induced structural phase transitions in a two-dimensional self-assembled network.

Two-dimensional (2D) supramolecular self-assembly at liquid-solid interfaces is a thermodynamically complex process producing a variety of structures. The formation of multiple network morphologies from the same molecular building blocks is a common occurrence. We use scanning tunnelling microscopy (STM) to investigate a structural phase transition between a densely packed and a porous phase of an alkylated dehydrobenzo[12]annulene (DBA) derivative physisorbed at a solvent-graphite interface. The influence of temperature and concentration are studied and the results combined using a thermodynamic model to measure enthalpy and entropy changes associated with the transition. These experimental results are compared to corresponding values obtained from simulations and theoretical calculations. This comparison highlights the importance of considering the solvent when modeling porous self-assembled networks. The results also demonstrate the power of using structural phase transitions to study the thermodynamics of these systems and will have implications for the development of predictive models for 2D self-assembly.

Characterization of fluorescence in heat-treated silver-exchanged zeolites.

Thermal treatment of Ag(+)-exchanged zeolites yields discrete highly photostable luminescent clusters without formation of metallic nanoparticles. Different types of emitters with characteristic luminescence colors are observed, depending on the nature of the cocation, the amount of exchanged silver, and the host topology. The dominant emission bands in LTA samples are situated around 550 and 690 nm for the samples with, respectively, low and high silver content, while in FAU-type materials only a broad band around 550 nm is observed, regardless of the degree of exchange. Analysis of the fluorescent properties in combination with ESR spectroscopy suggests that a Ag(6)(+) cluster with doublet electronic ground state is associated with the appearance of the 690-nm emitter, having a decay of a few hundred microseconds. Tentatively, the nanosecond-decaying 550-nm emitter is assigned to the Ag(3)(+) cluster. This new class of photostable luminescent particles with tunable emission colors offers interesting perspectives for various applications such as biocompatible labels for intracellular imaging.

Synthesis, Spectroscopy, Crystal Structure, Electrochemistry, and Quantum Chemical and Molecular Dynamics Calculations of a 3-Anilino Difluoroboron Dipyrromethene Dye

An asymmetrically substituted fluorescent difluoroboron dipyrromethene (BODIPY) dye, with a phenylamino group at the 3-position of the BODIPY chromophore, has been synthesized by nucleophilic substitution of 3,5-dichloro-8-(4-tolyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene. The solvent-dependent spectroscopic and photophysical properties have been investigated by means of UV-vis spectrophotometry and steady-state and time-resolved fluorometry and reflect the large effect of the anilino substituent on the fluorescence characteristics. The compound has a low fluorescence quantum yield in all but the apolar solvents cyclohexane, toluene, and chloroform. Its emission maxima in a series of solvents from cyclohexane to methanol are red-shifted by approximately 50 nm in comparison to classic BODIPY derivatives. Its oxidation potential in dichloromethane is at ca. 1.14 V versus Ag/AgCl. The absorption bandwidths and Stokes shifts are much larger than those of typical, symmetric difluoroboron dipyrromethene dyes. The values of the fluorescence rate constant are in the (1.4-1.7) x 10(8) s(-1) range and do not vary much between the solvents studied. X-ray diffraction analysis shows that the BODIPY core is planar. Molecular dynamics simulations show that there is no clear indication for aggregates in solution.

1,7-Disubstituted Boron Dipyrromethene (BODIPY) Dyes: Synthesis and Spectroscopic Properties

1,7-Dihalogenated boron dipyrromethene dyes were successfully synthesized and substituted, thus providing an entry to the final, elusive reactivity pattern. The spectroscopic properties of 1,7-disubstituted BODIPY dyes were studied and are discussed as a function of their structure.

Ratiometric, Fluorescent BODIPY Dye with Aza Crown Ether Functionality: Synthesis, Solvatochromism, and Metal Ion Complex Formation

A new pH and metal ion-responsive BODIPY-based fluorescent probe with an aza crown ether subunit has been synthesized via condensation of 4-(1,4,7,10-tetraoxa-13-aza-cyclopentadec-13-yl)-benzaldehyde with the appropriate 1,3,5,7-tetramethyl substituted boron dipyrromethene moiety. Steady-state and time-resolved fluorometries have been used to study the spectroscopic and photophysical characteristics of this probe in various solvents. The fluorescence properties of the dye are strongly solvent dependent: increasing the solvent polarity leads to lower fluorescence quantum yields and lifetimes, and the wavelength of maximum fluorescence emission shifts to the red. The Catalan solvent scales are found to be the most suitable for describing the solvatochromic shifts of the fluorescence emission. Fluorescence decay profiles of the dye can be described by a single-exponential fit in nonprotic solvents, whereas two decay times are found in alcohols. Protonation as well as complex formation with several metal ions are investigated in acetonitrile as solvent via fluorometric titrations. The aza crown ether dye undergoes a reversible (de)protonation reaction (pKa = 0.09) and shows a approximately 50 nm blue shift in the excitation spectra and a 10-fold fluorescence increase upon protonation. The compound also forms 1:1 complexes with several metal ions (Li(+), Na(+), Mg(2+), Ca(2+), Ba(2+), Zn(2+)), producing large blue shifts in the excitation spectra and significant cation-induced fluorescence amplifications.

Emerging Solvent‐Induced Homochirality by the Confinement of Achiral Molecules Against a Solid Surface

The unique handedness of chiral molecules affects chemical, physical, and biological phenomena. While observed in solution for helical polymers and self-assembled stacks of molecules, transmission of chiral information is particularly selective at ordered interfaces as a result of geometrical restrictions introduced by two-dimensional (2D) confinement. Chiral amplification of enantiomerically enriched mixtures has been demonstrated either by chemical reactions at the air–water interface, or upon self-assembly on solid surfaces. Homochirality in achiral enantiomorphous monolayers can be realized by merging chiral modifiers in the monolayer or by exposing monolayers to magnetic fields. Alternatively, the potential role of solvents in amplification of chirality and emergence of homochirality at surfaces remains unexplored to date. Herein we show how solvent-induced macroscopic chirality emerges within self-assemblies of achiral molecules on achiral surfaces. It is an exclusive surface-confined process, and as such it differs from “chiral-solvent-” or “chiral-guestinduced” chirality of supramolecular systems in solution. To demonstrate that homochirality emerges at the interface between a chiral liquid and the surface of highly oriented pyrolytic graphite (HOPG), we selected a hydrogen-bonding achiral diamino triazine oligo-(p-phenylenevinylene) oligomer (A-OPV4T, Figure 1). The chiral analogue, ((S)-OPV4T, Figure 1), was recently shown to assemble exclusively in a counter-clockwise (CCW) hydrogen-bonded rosette motif at the liquid–solid interface, with 1-phenyloctane as the achiral solvent. Molecular homochirality is expressed at the supramolecular level as a result of the 2D packing of the chiral rosette. The chiral solvent in the current study,

New picosecond laser system for easy tunability over the whole ultraviolet/visible/near infrared wavelength range based on flexible harmonic generation and optical parametric oscillation

A new laser-based and time-correlated single photon counting (TCSPC) detection system which allows easy and fast tuning of excitation wavelengths over a broad range from 240 to 1300 nm, with small gaps from 335 to 360 nm and 660 to 720 nm, has been built. The unique combination of a mode-locked Ti:sapphire laser, an optical parametric oscillator, pulse selectors, and harmonic generators delivers ultrafast laser pulses (1–2 ps) with variable repetition rates and excitation wavelengths. Performance characteristics of the laser system at different excitation wavelengths are reported and the TCSPC setup, which is characterized by a total instrument response function of 25 ps full width at half maximum, is described. Typical TCSPC measurements demonstrate the capability of the system of deriving decay or species associated excitation spectra.

Vicarious Nucleophilic Substitution of α-Hydrogen of BODIPY and Its Extension to Direct Ethenylation

Direct, oxidizer-free substitution of the 3-hydrogen of BODIPY derivatives has been established through a vicarious nucleophilic substitution procedure. This methodology has been combined with a reversible Michael addition on nitrostyrenes to provide a novel, highly efficient entry to the valuable 3-styrylated BODIPY dyes.

Photophysical study of bay substituted perylenediimides

A detailed investigation of the photophysical properties of a series of perylenediimide systems bearing three different types of bay substituents is presented. Single photon timing and femtosecond transient absorption experiments reveal that the dynamics of interconversion between two conformational arrangements of these substituents occurs with a time constant of 550 ps. In addition, charge transfer from the electron-rich units attached to the bay area of the electron-poor perylenediimide core is observed. This process leads to a fast non-radiative deactivation of the locally excited state of the perylenediimide in polar solvents. When the experimental results of the investigated systems are compared we observe a shift from a conformational dynamics towards competitive excited state processes involving charge transfer in the -meta and -para substituted perylenediimide chromophore.

Second-Harmonic Generation in GFP-like Proteins

The second-order nonlinear optical properties of green fluorescent proteins (GFPs), such as the photoswitchable Dronpa and enhanced GFP (EGFP), have been studied at both the theoretical and experimental levels. In the case of Dronpa, both approaches are consistent in showing the rather counterintuitive result of a larger second-order nonlinear polarizability (or first hyperpolarizability, beta) for the protonated state, which has a higher transition energy, than for the deprotonated, fluorescent state with its absorption at lower energy. Moreover, the value of beta for the protonated form of Dronpa is among the highest reported for proteins. In addition to the pH dependence, we have found a wavelength dependence in the beta values. These properties are essential for the practical use of Dronpa or other GFP-like fluorescent proteins as second-order nonlinear fluorophores for symmetry-sensitive nonlinear microscopy imaging and as nonlinear optical sensors for electrophysiological processes. An accurate value of the first hyperpolarizability is also essential for any qualitative analysis of the nonlinear images.