ИСТИНА

Anticrowns represent charge-reversed analogues of crown ethers and related species. Therefore, one might suggest that these macroheterocyclic antipodes containing several Lewis acidic and, correspondingly, several Lewis basic centers in the chain would readily react with each other. Indeed, we have found that the three-mercury anticrown (o-C6F4Hg)3 (1) is able to bind crown ethers with the formation of sandwich complexes. In the reaction of 1 with 1,3,5-trioxane the isolated 1:1 adduct has a cage structure. If the reactions of 1 with crown ethers are carried out in the presence of traces of water, novel sandwich adducts additionally containing coordinated molecules of H2O are formed. It has also been shown that the reactions of 1 with aqueous [18]crown-6 in methanol or acetone lead to self-assembly of unusual supramolecular aggregates in which the crown ether and water guests are sandwiched by two mutually parallel anticrown units while the solvent species are bonded to the Hg centres from the outer sides of the planes of the molecules of 1. The interaction of 1 with thiacrowns ([9]thiacrown-3 and 1,3,5-trithiane) in CH2Cl2 results in the formation of complexes having sandwich and cage structures, respectively. Anticrown 1 can also form complexes with azacrowns. One of such complexes, viz., the adduct of 1 with N,N,N-trimethyl-1,3,5-triazacyclohexane, has a unique double-cage structure. Interestingly, if the reaction of 1 with 1,4,8,11-tetraazacyclotetradecane (cyclam) is carried out in CH2Cl2, the subtraction of HCl from the solvent occurs and the sandwich complex {[(o-C6F4Hg)3]2Cl2}[(CH2)10(NH2)2(NH)2] containing two chloride anions and the molecule of diprotonated cyclam between the planes of the anticrown species is produced. This supramolecular ensemble is the first example of a complex wherein the anionic species is simultaneously coordinated with two types of anion receptors, namely with an anticrown and protonated azacrown.