Clar Goblet and Aromaticity Driven Multiradical Nanographenes

The Clar Goblet, the first radical bowtie nanographene proposed by Erich Clar nearly 50 years ago, was recently synthesized. Bowtie nanographenes present quasi-degenerate magnetic ground states, which make them so elusive as unique. A thorough analysis is presented of the spin-state energetics of Clar Goblet and bowtie nanographenes by a battery of existing and novel ab initio procedures ranging from density functional theory to complete active space Hamiltonians. With this, it was proven that π radicals of bowtie nanographenes sit on BP (Benzo[cd]Pyrene) moieties driven by their local aromaticity, a purely chemical concept, which confers global stability to the whole structure. Besides, a novel Pauli energy densities analysis provided a visual intuitive explanation for this preference. These findings allow envisioning that analogous bowtie nanographenes with arbitrary polyradical character are not only feasible at the molecular scale but will share Clar Goblet's peculiar properties.     

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.     

An efficient synthesis and cytotoxic activity of 2‐(4‐chlorophenyl)‐1H–benzo[d]imidazole obtained using a magnetically recyclable Fe3O4 nanocatalyst‐mediated white tea extract

A simple and efficient procedure has been developed for the synthesis of biologically relevant 2‐substituted benzimidazoles through a one‐pot condensation of o‐phenylenediamines with aryl aldehydes catalysed by iron oxide magnetic nanoparticles (Fe₃O₄ MNPs) in short reaction times with excellent yields. In the present study, Fe₃O₄ MNPs synthesized in a green manner using aqueous extract of white tea (Camelia sinensis) (Wt‐Fe₃O₄ MNPs) were applied as a magnetically separable heterogeneous nanocatalyst to synthesize 2‐(4‐chlorophenyl)‐1H–benzo[d]imidazole which has potential application in pharmacology and biological systems. Fourier transform infrared and NMR spectroscopies were used to characterize the 2‐(4‐chlorophenyl)‐1H–benzo[d]imidazole. In vitro cytotoxicity studies on MOLT‐4 cells showed a dose‐dependent toxicity with non‐toxic effect of 2‐(4‐chlorophenyl)‐1H–benzo[d]imidazole, up to a concentration of 0.147 µM. The green synthesized Wt‐Fe₃O₄ MNPs as recyclable nanocatalyst could be used for further research on the synthesis of therapeutic materials, particularly in nanomedicine, to assist in the treatment of cancer.     

Accessing Extended Fused Isoindolinones Via Sequential Anionic Intramolecular Cyclizations

Sequential anionic intramolecular cyclizations and modelling were used for the first time to access unusual fused heterocyclic frameworks in excellent yields. 5-Exo-dig cyclizations yielded isoindolinone motifs and a subsequent 6-exo- and 7-endo-dig cyclization was directed to provide either fused isoquinoline or azepine frameworks. Regioselectivities were controlled by exploiting stereoelectronic effects via n_C−→π*_(Ph) interactions, and modelling studies provided reaction scope.     

Quaterthiophene-based dimers containing an ethylene bridge: molecular design,synthesis, and optoelectronic properties

Two quaterthiophene-based dimers including an ethylene bridge have been designed and efficiently prepared; experimental and computational studies show a promising potential as semiconducting material with a charge transport of higher dimensionality compared to quaterthiophene.