18-crown-6 ether complexes with aralkylammonium perchlorates

Thermochemical properties of crown ether complexes have been studied by simultaneous TG-DTA (thermogravimetric analysis-differential thermal analysis) coupled with a mass spectrometer, DSC (differential scanning calorimetry) and hot stage microscopy (HSM). The examined complexes contain benzylammonium- [BA], (R)-(+)-a-phenylethylammonium- [(R)-PEA], (R)-(+)- and (S)-(-)-a-(1-naphthyl)ethylammonium perchlorate [(R)-NEA and (S)-NEA] salts as guests. In the cases of BA and (R)-PEA an achiral pyridono-18-crown-6 ligand [P18C6], and in the case of (R)-NEA and (S)-NEA a chiral (R,R)-dimethylphenazino-18-crown-6 ligand [(R,R)-DMPh18C6] was used as host molecule to obtain four different crown ether complexes. In all cases, the melting points of the complexes were higher than those of both the host and the guest compounds. The decomposition of the complexes begins immediately after their melting is completed, while the BA and (R)-PEA salts and the crown ether ligands are thermally stable by 50 to 100 K above their melting points. During the decomposition of the salts and the four complexes strongly exothermic processes can be observed which are due to oxidative reactions of the perchlorate anion. Ammonium perchlorate crystals were identified among the decomposition residues of the salts. P18C6 was observed to crystallize with two molecules of water. The studied complexes of P18C6 did not contain any solvate. BA was observed to exhibit a reversible solid-solid phase transition upon heating. The heterochiral complex consisting of (S)-NEA and (R,R)-DMPh18C6 shows a solid-solid phase transition followed by two melting points. HSM observations identified three crystal modifications, two of them simultaneously co-existing. This revised version was published online in July 2006 with corrections to the Cover Date.