METHYL ARYL KETONES IN THE SYNTHESIS OF HEXAAZABICYCLOICOSANE CAGE COMPLEXES

The template syntheses of various Co-III-hexaazaicosane-type cage comp lexes with aromatic substituents are described. The parent template, [ Co(sen)](3+) ion {sen = 4,4',4 ''-ethylidynetris(3-azabutan-1-amine)}, paraformaldehyde, a methyl aryl ketone and a base were reacted in ace tonitrile to give aroyl substituents attached to the fully saturated s arcophagine cage thyl-3,6,10,13,16,19-hexaazabicyclo[6.6.6]-icosane co balt(III) ion) and aryl substituents attached to an analogous imine-ty pe cage l-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosa-2-ene cobalt(III) ion). Phenyl, napthyl, phenanthryl, anthracenyl and anthraquinonyl su bstituents have been bound to the cage simply by this route to give mo lecules that can act as intercalators in DNA or as photosensitizers at tached to reversible redox-active metal centres and can couple an orga nic two-electron reagent with an inorganic one-electron reagent. An X- ray crystallographic analysis of a phenanthroyl cage complex has also been carried out. These substances and their progeny should be useful as biological probes and fluorescent indicators and for energy capture and conversion.