First integrals for Finsler metrics with vanishing $$\chi $$ -curvature

Annals of Global Analysis and Geometry - We prove that in a Finsler manifold with vanishing $$\chi $$ -curvature (in particular with constant flag curvature) some non-Riemannian geometric...     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

Two-Photon Absorption and Cell Imaging of Fluorene-Functionalized Epicocconone Analogues

Epicocconone 1 is a natural chromophore isolated from the fungus Epicoccum nigrum that has shown applications in proteomics and fluorescent microscopy thanks to its unique pro-fluorescence properties. The modification of the skeleton of the natural product by replacing the triene side chain by a fluorenyl scaffold can noticeably increase the fluorophore's absorption coefficient. The synthesis of the analogues of the natural product has been made possible by the use of a palladium-catalyzed carbonylation reaction, allowing the construction of the β-keto-dioxinone key intermediate. Two-photon absorption cross-section measurements of the fluorenyl epicocconone analogues show a structure dependency with values ranging from 60 to 280 GM and live cell imaging show intense staining of intracellular vesicle-like structures around the nucleus.     

New Penta(tetrathiafulvalenyl)[60]fullerenes for Supramolecular Materials

New penta(organo)fullerenes donor–acceptor systems bearing five tetrathiafulvalene recognition units have been synthesized to promote self‐assemblies similar in appearance to shuttlecocks nested into each other thanks to the conical host cavity created around the fullerene together with the π–π and electronic interactions.     

Bis(N‐Confused Porphyrin) as a Semirigid Receptor with a Chirality Memory: A Two‐Way Host Enantiomerization through Point‐to‐Axial Chirality Transfer

The adduct formation of protonated bis(N‐confused porphyrin) (BNCP, 3,3′‐bis(meso‐tetratolyl‐2‐aza‐21‐carbaporphyrin) with chiral anions, carboxylic acids, and alcohols was studied in solution by means of ¹H NMR and circular dichroism (CD) spectroscopic analysis and DFT methods. The addition of enantiopure guests to the acidified BNCP resulted in optical activity that vanished after neutralization. Pairs of the ¹H NMR‐distinguishable diastereomers were formed when enantiopure guests were applied, although a single form was observed upon the addition of the racemic mixtures in each case. Unidirectional configuration change that led to diastereomeric excess was observed in several instances. Such an excess was memorized by metalation of the adducts with AgBF₄, thus resulting in optically active silver(III) complexes of BNCP with some enantiomeric excess. Absolute configurations of BNCP cations and bis(zinc) and bis(silver(III)) complexes were determined on the basis of time‐dependent (TD)‐DFT calculations of their CD spectra. It was shown that some of the chiral carboxylates induced opposite directions of enantiomerization of di‐ and tetracations or di‐/tetracation and bis(zinc) complexes. The source of the optical activity of the equimolar diastereomeric mixture of adducts is discussed.     

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π‐conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large‐scale synthesis of protected quarter‐, sexi‐, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single‐crystal X‐ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide‐substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.     

Extreme-field physics in Penning traps

We present two Penning trap experiments concerned with different aspects of the physics of extreme electromagnetic fields, the ARTEMIS experiment designed for bound-electron magnetic moment measurements in the presence of the extremely strong fields close to the nucleus of highly charged ions, and the HILITE experiment, in which well-defined ion targets are to be subjected to high-intensity laser fields.