Synthesis, structural studies and photochemistry of cobalt(III) complexes of anthracenylcyclam macrocycles

This work reports the syntheses, structures and some photochemistry in DMF of the cobalt complexes trans-[Co-III(2) Cl-2] Cl . 0.5CH(3)OH and trans-[Co-III(3) Cl-2] Cl . 4H(2)O, where 2 is 6-(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane- 5,7-dione and 3 is 6-(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane. In the preparation of the macrocyclic ligand, 3, the formation of a polycyclic bis(aminal) intermediate and its subsequent acid hydrolysis to 3 is a cleaner route than the traditional procedure in which the analogous dioxocyclam 2 is reduced with borane reagents. The crystal structure of trans-[Co-III(3) Cl-2] Cl . 4H(2)O shows that the macrocycle adopts the trans-III conformation, in which the anthracene moiety is extended away from the cobalt ion and the anthracene to Co separation is 7.22 Angstrom. For the related complex trans-[Co-III(2) Cl-2] Cl . 0.5CH(3)OH, however, the anthracene is bent over the highly conjugated tetracycle and significant interactions between the anthracene and the complex occur. A novel new complex, trans-[Co(12)Cl-2] (where 12 is 5,7-hydroxy-6-oxo-1,4,8,11-tetraazacyclotetradecane-4,7-diene) which is a degradation product of the complex trans-[Co-III(2) Cl-2] Cl is also reported.