The strong Lewis acid tungsten oxo complex of calix[4]arene can be obtained in both hydrated and non-hydrated forms. This complex coordinates a water molecule inside the cavity via strong O···W interactions with relatively short distances of 2.284(4) and 2.329(2) Å for the tungsten oxo complex of calix[4]arene··H2O·aniline (1), and the tungsten oxo complex of calix[4]arene·H2O·toluene (2·toluene), respectively. The strong interactions are also deduced by the relatively high H2O elimination temperature observed by TGA and DSC (above 200 °C). The coordinated water molecule inside the calix[4]arene cavity is characterized by a strong IR absorption at 3616 cm1, and a narrow resonance at ~1.2 ppm (the chemical shifts of the uncoordinated water are 1.55 and 1.60 ppm in C6D6 and CDCl3, respectively). This water molecule gives rise to H-bonds with aniline in 1. The tungsten oxo complex of 5,11,17,23-tetrabromocalix[4]arene (4), also binds H2O as the characteristic signatures are observed. The successful removal of H2O in 2, is performed under mild conditions using bis(tetrahydrofuran)-uranyl nitrate as a competitive Lewis acid. When this reaction is performed in acetonitrile, butyronitrile or tert-butylnitrile, the corresponding tungsten oxo complexes of calix[4]arene·acetonitrile (3), ·butyronitrile (5), and ·tert-butylnitrile (6) are obtained. The use of uranyl as a H2O abstractor is unprecedented. The X-ray structure of 3 consists of a tungsten oxo complex of calix[4]arene coordinated by an acetonitrile molecule (d(W···N = 2.412(2) Å). The tetra-5,11,17,23-choromethyl-25,26,27,28-tetrahydroxycalix[4]arene reacts with M(O)Cl4 (M = Mo, W) in a 1:1 stoichiometry, via a tetra FriedelCrafts addition of benzene or toluene, followed by a lower-rim complexation of the metal oxide, to form "flower-shaped" calix[4]arenes. This "one pot" double functionalization is unprecedented.Key words: calix[4]arene, tungsten, molybdenum, X-ray, hostguest, FriedelCrafts, Lewis acid, uranyl, DSC, TGA.
Al(ORF)3 (RF = C(CF3)3) activated silica: a well-defined weakly coordinating surface anion