ИСТИНА

Anticrowns represent charge-reverse antipodes of crown ethers and their thia and aza analogues. Therefore, one might suggest that these remarkable species would readily form complexes with each other. Indeed, it was found that the three-mercury anticrown (o-C6F4Hg)3 (1) is able to bind crown ethers with formation of sandwich complexes. In the case of 1,3,5-trioxane isolated compound have cage structure. If these reactions of 1 with crown ethers are held in the presence of traces of water, novel sandwich adducts additionally containing coordinated molecules of H2O are formed. Moreover, the reaction of 1 with aqueous [18]crown-6 in methanol or acetone leads to self-assembly of unusual supramolecular aggregates in which the crown ether and water guests are sandwiched by two mutually parallel anticrown moieties while the solvent molecules are coordinated with Hg centres from the outer sides of the planes of 1. The interaction of macrocycle 1 with thiacrowns ([9]thiacrown-3 and 1,3,5-trithiane) in methylene dichloride results in complexes having sandwich and cage structures, respectively. Anticrown 1 could also form complexes with azacrowns. One of them, the adduct of 1 with N,N,N-trimethyl-1,3,5-triazacyclohexane, have an unique double-cage structure. Interestingly, it turned out that if the reaction of 1 with cyclam is carried out in CH2Cl2, the subtraction of HCl from the solvent occurs and the complexes {[(o-C6F4Hg)3]nCl2}[(CH2)10(NH2)2(NH)2] (n = 1, 2) are formed, depending on experimental conditions. These supramolecular ensembles are the first examples of anion coordination by two types of anion receptors: anticrowns and protonated azacrowns.