Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

Abstract

1,2-bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper-catalyzed coupling of aminated nickel(II) 5,10-diarylporphyrin ("corner porphyrin") and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso-positions in a trans-like orientation, and the other with a cis-like disposition. The free meso-positions of the obtained dimer have been further functionalized while the synthesis of a zinc analog has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.