Synthesis and Spectroscopic Properties of Symmetrically Tetrasubstituted Phthalocyanines with Four Alkyl or Aryl Chains or Porphyrin, Adamantane, Crown, or Quinone Units Attached

Symmetrically tetrasubstituted phthalocyanines (Pcs) with four alkyl or aryl chains or adamantane, quinone, porphyrin, or crown units attached have been synthesized, and some of their spectroscopic properties are reported. These Pcs have been synthesized from the tetraanhydrides of metalated or nonmetalated 2,3,9,10,16,17,23,24-octacarboxyPcs and primary amines by one-step reaction in N-methyl-2-pyrrolidone. Differing from previously reported tetrasubstituted Pcs, the resultant Pcs do not generally contain positional isomers. They have a very high tendency toward aggregation, and as a result, their absorption spectra are unique in that the intensity of the Q band is extraordinally weak and its tail stretches to ca. 800 (Mt = Cu), 900 (Mt = H₂), 1000 (Mt = Fe), or 1200 (Mt = Co) nm. Some interaction between the substituent groups and Pc moiety was confirmed spectroscopically in quinone and porphyrin attached Pcs. A zinc complex showed S₂ emission in addition to S₁ emission.