A Water-Soluble Cryptophane Decorated with Aromatic Amine Groups Shows High Affinity for Cesium and Thallium(I).

An anti-cryptophane decorated with three aromatic amine and three phenol groups shows a high affinity for the cesium and thallium cations in LiOH/H2O (0.1 M). The formation of the complexes was studied by 133Cs NMR and by 205Tl NMR spectroscopy at different temperatures. Characteristic signals for caged cesium and thallium were observed at a high field with respect to the signals of the free cations present in the bulk. Isothermal titration calorimetric experiments performed in LiOH/H2O (0.1 M) and NaOH/KCl buffer (pH = 13) allowed us to determine the parameter of complexation and to ascertain the high affinity of this cryptophane for cesium and thallium. A comparison with other cryptophanes that bind these two cations shows that the introduction of nitrogen atoms into the cryptophane backbone has an effect on the binding properties. The affinity for cesium and thallium(I) ions is in the following order of substitution: OH > NH2 > OCH2COOH. This study paves the way to the design of new efficient host molecules for the extraction of these two cations in aqueous solution.

Study of syn and anti Xenon-Cryptophanes Complexes Decorated with Aromatic Amine Groups: Chemical Platforms for Accessing New Cryptophanes.

We report the synthesis of C3-symmetric cryptophanes decorated with three aromatic amine groups on the same CTB cap and their interaction with xenon. The relative stereochemistry of these two stereoisomers syn and anti was assessed thanks to the determination of the X-ray structure of an intermediate compound. As previously observed with the tris-aza-cryptophanes analogs anti-1 and syn-2 (J. Org. Chem. 2021, 86, 11, 7648-7658), both compounds anti-5 and syn-6 show a slow in-out exchange dynamics of xenon at 11.7 T. Our work supports the idea that the presence of nitrogen atoms grafted directly onto the cryptophane backbone has a strong impact on the in-out exchange dynamics of xenon whatever their stereochemistry. This result contrasts with the case of other cryptophanes decorated solely with methoxy substituents. Finally, we demonstrate that these new derivatives can be used to design new anti/syn cryptophanes bearing suitable ligands in order to constitute potent 129Xe NMR-based sensors. An example is reported here with the synthesis of the tris-iodo derivatives anti-13 and syn-14 from compounds anti-5 and syn-6.

Are the Physical Properties of Xe@Cryptophane Complexes Easily Predictable? The Case of syn- and anti-Tris-aza-Cryptophanes.

We report the synthesis and optical resolution of C3-symmetrical tris-aza-cryptophanes anti-3 and syn-4, as well as the study of their interaction with xenon via hyperpolarized 129Xe NMR. These molecular cages are close structural analogues of the two well-known cryptophane-A (1; chiral) and cryptophane-B (2; achiral) diastereomers since these new compounds differ only by the presence of three nitrogen atoms grafted onto 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 calculations at the density functional theory level and vibrational circular dichroism spectroscopy. More importantly, our results show that despite the large structural similarities with cryptophane-A (1) and -B (2), these two new compounds show a very different behavior in the presence of xenon in organic solutions. These results demonstrate that prediction of the physical properties of the xenon@cryptophane complexes, only based on structural parameters, remains extremely difficult.

Synthesis of Tetraarylethene Luminogens by C-H Vinylation of Aromatic Compounds with Triazenes.

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.