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

Alison M. Funston, Kenneth P. Ghiggino, Martin J. Grannas, W. David McFadyen, Peter A. Tregloan

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18 Citations (Scopus)


This work reports the syntheses, structures and some photochemistry in DMF of the cobalt complexes trans-[CoIII(2)Cl2]Cl·0.5CH3OH and trans-[CoIII(3)Cl2]Cl·4H2O, 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-[CoIII(3)Cl2]Cl·4H2O 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 Å. For the related complex trans-[CoIII(2)Cl2]Cl·0.5CH3OH, 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)Cl2] (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-[CoIII(2)Cl2]Cl is also reported.

Original languageEnglish
Pages (from-to)3704-3712
Number of pages9
Journal Journal of the Chemical Society - Dalton Transactions
Issue number19
Publication statusPublished - 25 Sep 2003


  • Cobalt
  • Macrocycles
  • Photochemistry
  • Structual studies
  • X-ray diffraction, X-ray powder diffraction

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