Tetraarylethenes are obtained by acid‐induced coupling of vinyl triazenes with aromatic compounds. This new C−H activation route for the synthesis of aggregation‐induced emission luminogens is simple, fast, and versatile. It allows the direct grafting of triarylethenyl groups onto a variety of aromatic compounds, including heterocycles, supramolecular hosts, biologically relevant molecules, and commercial polymers.
We report the synthesis and the optical resolution of C3-symmetrical tris-azacryptophanes anti-3 and syn-4, as well as the study of their interaction with xenon via hyperpolarized 129 Xe NMR. These molecular cages are close structural analogs of the two wellknown cryptophane-A (1; chiral) and cryptophane-B (2; achiral) diastereomers since these new compounds differ only by the presence of three nitrogen atoms grafted on the same cyclotribenzylene unit. The assignment of their relative (syn vs anti) and absolute configurations was made possible thanks to the combined use of quantum calculation at the DFT level and vibrational circular dichroism (VCD). More importantly, our results show that despite the large structural similarities with cryptophane-A (1) and -B (2), these two new compounds show very different behavior in the presence of xenon in organic solution. These results demonstrate that a prediction of the physical properties of the xenon@cryptophane complexes, only based on structural parameters, remains extremely difficult.
Metallosupramolecular assemblies of the general formula M2nLn can adopt prismatic or cage‐like structures. The factors controlling the aggregation number n and the geometry of the final assembly are still not fully understood. Here, we describe the synthesis and the structural characterization of PtII8L4 complexes, which adopt tetragonal prismatic structures. The bridging ligand L features four pyridyl groups and an inert FeII clathrochelate complex at its core. Furthermore, the ligand has three phenanthrene groups, which are attached to the FeII complex in a divergent fashion. These polyaromatic side groups control the self‐assembly process by promoting the formation of a structure, which allows for an energetically favorable packing of the aromatic groups. Replacing the phenanthrene groups on the ligand by aliphatic n‐butyl groups results in a complete change of geometry: instead of tetragonal prisms, PtII8L4 complexes with cage‐like structures are observed.
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