Substitution, dimerization, metalation, and ring-opening reactions of N-fused porphyrins

A variety of reactions such as substitution, dimerization, rhenium(I) metalation, and ring-opening reactions of N-fused porphyrin (NFP) and optical properties of the products are presented. Palladium-catalyzed cross-coupling reactions under Suzuki or Stille conditions afford aryl and arylethynyl-substituted NFPs (12, 14) and an ethynyl-bridged dimer (15) from 3-bromo-substituted NFP (3b) in 40–98% yields. Treatment of NFP with silver(I) trifluoroacetate in CHCl3 affords a dimer (22) linked at both C21-positions of the fused rings and its bis-Re(I) metal complex (24) is synthesized. X-ray structures of the 3-trifluoromethyl and 3-phenyl NFP derivatives (9e and 12a) reveal the three-center hydrogen bondings in the core. All the new NFP derivatives display unique absorption spectra, and particularly, ethyne-bridged NFP-dimer (15) shows a remarkable bathochromic shift into a near-infrared region showing an absorption band at 1020 nm with tailing up to 1100 nm. Moreover, alkoxide nucleophiles convert NFP into NCP derivatives by the cleavage of C–N bond in the fused ring, which is useful for the preparation of various C3-substituted NCPs and C21,C21′-linked NCP dimers from NFPs.