The synthesis of shape‐persistent organic cage compounds is often based on the usage of multiple dynamic covalent bond formation (such as imines) of readily available precursors. By careful choice of the precursors geometry, the geometry and size of the resulting cage can be accurately designed and indeed a number of different geometries and sizes have been realized to date. Despite of this fact, little is known about the precursors conformational rigidity and steric preorganization of reacting functional groups on the outcome of the reaction. Herein, the influence of conformational rigidity in the precursors on the formation of a [4+4] imine cage with truncated tetrahedral geometry is discussed.

In contrast to organic cages which are formed by exploiting dynamic covalent chemistry, such as boronic ester cages, imine cages, or disulfide cages, those with a fully carbonaceous backbone are rarer. With the exception of alkyne metathesis based approaches, the vast majority of hydrocarbon cages need to be synthesized by kinetically controlled bond formation. This strategy implies a multiple step synthesis and no correction mechanism in the final macrocyclization step, both of which are responsible for low overall yields. Whereas for smaller cages the intrinsic drawbacks are not always obvious, larger cages are seldom synthesized in yields beyond a few tenths of a percent. Presented herein is a three‐step method to convert imine cages into hydrocarbon cages. The method has been successfully applied to even larger structures such as derivatives of C 72 H 72 , an unknown cage suggested by Fritz Vögtle more than 20 years ago.

The pollution of groundwater with nitrate is a serious issue because nitrate can cause several diseases such as methemoglobinemia or cancer. Therefore, selective removal of nitrate by efficient binding to supramolecular hosts is highly desired. Here we describe how to make [2 + 3] amide cages in very high to quantitative yields by applying an optimized Pinnick oxidation protocol for the conversion of corresponding imine cages. By NMR titration experiments of the eight different [2 + 3] amide cages with nitrate, chloride and hydrogen sulfate we identified one cage with an unprecedented high selectivity towards nitrate binding vs. chloride (S = 705) or hydrogensulfate (S > 13500) in CD 2 Cl 2 / CD 3 CN (1 : 3). NMR experiments as well as single-crystal structure comparison of host-guest complexes give insight into structure-property-relationships.

Three shape‐persistent [4+4] imine cages with truncated tetrahedral geometry with different window sizes were studied as hosts for the encapsulation of tetra‐n‐alkylammonium salts of various bulkiness. In various solvents the cages behave differently. For instance, in dichloromethane the cage with smallest window size takes up NEt4+ but not NMe4+, which is in contrast to the two cages with larger windows hosting both ions. To find out the reason for this, kinetic experiments were carried out to determine the velocity of uptake but also to deduce the activation barriers for these processes. To support the experimental results, calculations for the guest uptakes have been performed by molecular mechanics’ simulations. Finally, the complexation of pharmaceutical interested compounds, such as acetylcholine, muscarine or denatonium have been determined by NMR experiments.

In contrast to organic cages which are formed by exploiting dynamic covalent chemistry, such as boronic ester cages, imine cages, or disulfide cages, those with a fully carbonaceous backbone are rarer. With the exception of alkyne metathesis based approaches, the vast majority of hydrocarbon cages need to be synthesized by kinetically controlled bond formation. This strategy implies a multiple step synthesis and no correction mechanism in the final macrocyclization step, both of which are responsible for low overall yields. Whereas for smaller cages the intrinsic drawbacks are not always obvious, larger cages are seldom synthesized in yields beyond a few tenths of a percent. Presented herein is a three‐step method to convert imine cages into hydrocarbon cages. The method has been successfully applied to even larger structures such as derivatives of C72H72 , an unknown cage suggested by Fritz Vögtle more than 20 years ago.

The Cover Feature shows the molecular structure (spacefill model; atoms of hydrogen are depicted in white, carbon in grey, nitrogen in blue, oxygen in bright red, and bromine in red) of the nanobelt synthesized by Lauer and colleagues. The nanobelt “swims” in a sea of many other oligomeric, polymeric, and monomeric structures and is “fished out” selectively by gel permeation chromatography, represented by a fishing hook. More information can be found in the Full Paper by M. Mastalerz et al.

Triptycenes with their predefined D 3h -symmetry are excellent molecular building blocks to construct shape-persistent nanobelts having π-orbitals orthogonal to the ring plane. However, up to now, there are only a very few examples of fused and rigid iptycene nanobelts synthesized in several consecutive steps in overall yields below 1 %. Here we present the simple one-step one-pot approach to an iptycene nanobelt, which forms in > 2 % and can readily be isolated from the polymeric by-product by gel-permeation chromatography.