The application of design of experiments (DoE) reaction optimisation and solvent selection in the development of new synthetic chemistry

This article outlines the benefits of using 'Design of Experiments' (DoE) optimisation during the development of new synthetic methodology. A particularly important factor in the development of new chemical reactions is the choice of solvent which can often drastically alter the efficiency and selectivity of a process. Whilst solvent optimisation is usually done in a non-systematic way based upon a chemist's intuition and previous laboratory experience, we illustrate how optimisation of the solvent for a reaction can be carried out by using a 'map of solvent space' in a DoE optimisation. A new solvent map has been developed specifically for optimisation of new chemical reactions using principle component analysis (PCA) incorporating 136 solvents with a wide range of properties. The new solvent map has been used to identify safer alternatives to toxic/hazardous solvents, and also in the optimisation of an SNAr reaction

Doubly Encapsulated Perylene Diimides: Effect of Molecular Encapsulation on Photophysical Properties

Intermolecular interactions play a fundamental role on the performance of conjugated materials in organic electronic devices, as they heavily influence their optoelectronic properties. Synthetic control over the solid state properties of organic optoelectronic materials is crucial to access real life applications. Perylene diimides (PDIs) are one of the most highly studied classes of organic fluorescent dyes. In the solid state, π–π stacking suppresses their emission, limiting their use in a variety of applications. Here, we report the synthesis of a novel PDI dye that is encapsulated by four alkylene straps. X-ray crystallography indicates that intermolecular π–π stacking is completely suppressed in the crystalline state. This is further validated by the photophysical properties of the dye in both solution and solid state and supported by theoretical calculations. However, we find that the introduction of the encapsulating “arms” results in the creation of charge-transfer states which modify the excited state properties. This article demonstrates that molecular encapsulation can be used as a powerful tool to tune intermolecular interactions and thereby gain an extra level of control over the solid state properties of organic optoelectronic materials

4d-inner-shell ionization of Xe+ ions and subsequent Auger decay

We have studied Xe+4d inner-shell photoionization in a direct experiment on Xe+ ions, merging an ion and a photon beam and detecting the ejected electrons with a cylindrical mirror analyzer. The measured 4d photoelectron spectrum is compared to the 4d core valence double ionization spectrum of the neutral Xe atom, obtained with a magnetic bottle spectrometer. This multicoincidence experiment gives access to the spectroscopy of the individual Xe2+4d−15p−1 states and to their respective Auger decays, which are found to present a strong selectivity. The experimental results are interpreted with the help of ab initio calculations.1\. Auflag

Potential Energy Surface Reconstruction and Lifetime Determination of Molecular Double-Core-Hole States in the Hard X-Ray Regime

A combination of resonant inelastic x-ray scattering and resonant Auger spectroscopy provides complementary information on the dynamic response of resonantly excited molecules. This is exemplified for CH3I, for which we reconstruct the potential energy surface of the dissociative I 3d−2 double- core-hole state and determine its lifetime. The proposed method holds a strong potential for monitoring the hard x-ray induced electron and nuclear dynamic response of core-excited molecules containing heavy elements, where ab initio calculations of potential energy surfaces and lifetimes remain challenging

Highly Luminescent Encapsulated Narrow Bandgap Polymers Based on Diketopyrrolopyrrole

We present the synthesis and characterisation of a series of encap-sulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intra-molecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone co-linearity as evidenced by STM. This study paves the way for DPP to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conju-gated polymers

Quenching of the 2pnd ¹P^o doubly excited states of helium by a dc electric field

The fluorescence yield quenching of low-lying doubly excited 2pnd 1Po states is observed to depend strongly on a dc electric field strength and its orientation with respect to the polarization of the incoming photon beam. The reduction of the yield accompanied by the lifetime shortening is attributed to the Stark mixing with the neighboring 2sns 1Se states, which redirects the 2pnd 1Po decay to the prompt autoionization channel. For n≥4, the lifetimes decrease from several hundred picoseconds down to several tens of picoseconds when an electric field in the kV/cm range is applied parallel to the photon probe polarization. Practically no lifetime change is observed for polarization perpendicular to the electric field direction. The results of the complex-scaling calculations are in a good agreement with the experimental data

Fingerprinting mean composition of lithium polysulfide standard solutions by applying high energy resolution fluorescence detected X-ray Absorption Spectroscopy

International audienceIn a lithium/sulfur (Li/S) battery, the reduction of sulfur along discharge involves a particular mechanism, where the active material successively dissolves into the electrolyte to form lithium polysulfides intermediate species (Li2Sx), with x being a function of state of charge. In this work, sulfur K-edge Resonant Inelastic X-ray Scattering measurements were applied for the characterization of different Li2Sx polysulfide standard solutions. High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy allowed to separate clearly the pre-edge absorption peak corresponding to terminal sulfur atoms from the main absorption peak due to internal atoms, and to evaluate quantitatively the evolution of the peak area ratio as a function of the polysulfide chain length. Results of this experimental work demonstrate that the normalized area of the pre-edge is a reliable fingerprint of Li2Sx mean chain length in agreement with recent theoretical predictions. As a perspective, this work confirms that operando HERFD XAS can be used to differentiate polysulfides mean composition, which is key issue in the characterization of Li/S cells

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H 2 O

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Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions

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A modified magnetic bottle electron spectrometer for the detection of multiply charged ions in coincidence with all correlated electrons: decay pathways to Xe 3+ above xenon-4d ionization threshold

International audienceNew magnet design of a magnetic bottle electron spectrometer allowing the detection of multiply charged ions in coincidence with n electrons. Electrons spectra obtained without and with filtering by coincidence with Xe n + ions