Sumanene-carbazole conjugate with push-pull structure and its chemoreceptor application.

The first-of-its-kind tetra-substituted sumanene derivative, featuring the push-pull chromophore architecture, has been successfully designed. The inclusion of both strong electron-withdrawing (CF3) and electron-donating (carbazole) moieties in this buckybowl compound has enhanced the charge transfer characteristics of the molecule. This enhancement was supported by ultraviolet-visible (UV-Vis) and emission spectra analyses along with density functional theory (DFT) calculations. The application of the title sumanene-carbazole push-pull chromophore as a selective recognition material for cesium cations (Cs+) was also presented. The title compound exhibited effective and selective Cs+-trapping ability, characterized by a high apparent binding constant value (at the level of 105) and a low limit of detection (0.09-0.13 µM). Owing to the tuned optical properties of the title push-pull chromophore, this study marks the first time in sumanene-tethered chemoreceptor chemistry where efficient tracking of Cs+ binding was possible with both absorption and fluorescence spectroscopies. This work introduces a new approach toward tuning the structure of bowl-shaped optical chemoreceptors.

Design of a D3h-symmetry prismatic tris-(ferrocene-1,1'-diyl) molecular cage bearing boronate ester linkages.

This paper presents a simple, highly selective, and efficient (isolated yield of 68%) synthesis of a novel D3h-symmetry prismatic tris-(ferrocene-1,1'-diyl) organic cage (FcB-cage) by incorporating a boronate ester as a linkage motif. 1,1'-Diboronated derivatives of ferrocene and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) were used as the starting materials. The synthesized cage was comprehensively characterized by spectroscopic and microscopic methods, powder X-ray diffraction, thermogravimetry and voltammetry. Cyclic voltammetry analysis revealed the electronic communication between the ferrocene units of the FcB-cage. In addition, to better understand the mechanism behind the synthesis of such a cage, as well as its geometric properties, we performed DFT calculations.

Fast, solvent-free synthesis of ferrocene-containing organic cages via dynamic covalent chemistry in the solid state.

A simple, solvent-free synthetic protocol towards the synthesis of organic self-assembled macromolecules has been established. By employing mechanochemistry using glassware readily available to every organic chemist, we were able to synthesise three novel organic cage compounds exemplarily and to speed up the synthesis of a ferrocene-containing macrocycle by a factor of 288 compared to the solution-based synthesis. The structural investigation of the newly synthesised cages revealed different modes of connectivity from using ferrocene-containing aldehydes caused by the free rotation of the cyclopentadienyl units against each other. By extending the facile solvent-free synthesis to ball-milling, even compounds that show lower reactivity could be employed in the dynamic covalent formation of organometallic cage compounds. The presented protocol gives access to otherwise inaccessible structures, speeds up general synthetic workflows, and simultaneously reduces the environmental impact of supramolecular syntheses.