Porphyrinoids with Vinylene Bridges

Abstract

Porphyrinoids containing vinylene bridges, such as triphyrin(2.1.1), porphycene, porphyrin(2.1.2.1), and hexaphyrin(2.1.2.1.2.1), are a relatively new family of porphyrinoids. Vinylene bridges give porphyrinoids a lower symmetry and a flexibility of the framework and they permit cis/trans-isomerization reactions; these factors confer unique properties to these substances, such as coordination to metal ions and aromaticity switching. In this account, the synthesis, crystal structures, and properties of new porphyrinoids containing vinylene bridges are summarized.1 Introduction2 Triphyrin(2.1.1)3 Porphycene4 Porphyrin(2.1.2.1)5 Hexaphyrin(2.1.2.1.2.1)6 Conclusion

Recent advances in subphthalocyanines and related subporphyrinoids

“…668 Synthetic aspects and spectroscopic properties of [14]triphyrins(2.1.1) have been previously reviewed by some of us, 1 and others. 5,649,669,670 The synthesis of [14]triphyrins(2.1.1) can be performed in one step with 10-40% yields, by condensation reaction between a pyrrole n (Scheme 62, method A) and an aryl aldehyde in the presence of high concentration (1.2 equivalents) of BF 3 ÁOEt 2 . 668 An azafulvene or an azafulvenium cation have been proposed as feasible intermediates of the cyclization reaction to assemble the triphyrin(2.1.1) ring.…”

“…668 Synthetic aspects and spectroscopic properties of [14]triphyrins(2.1.1) have been previously reviewed by some of us, 1 and others. 5,649,669,670…”