Dihydroxy‐ and Tetrahydroxydicarbahemiporphyrazine: Phthalocyanine Analogues with Phenol and Resorcinol Units

Abstract

Abstract The synthesis of the phthalocyanine variant dicarbahemiporphyrazine ( 1 ) follows a simple Schiff base condensation protocol, and can be readily modified to incorporate a variety of modified benzene rings into the macrocycle. In this report, we present the synthesis of dihydroxydicarbahemiporphyrazine ( 2 ) and tetrahydroxydicarbahemiporphyrazine ( 3 ), hemiporphyrazines in which two phenol and two resorcinol groups, respectively, have been incorporated into the backbone of the macrocycle. The structures of the two macrocycles have been elucidated by X‐ray diffraction, and both adopt planar conformations due to the tautomerization of the internal hydrogen atoms to meso nitrogen positions. The Ag I complexes of both rings are also presented, and the structures of both complexes Ag 2 and Ag 3 have also been elucidated by single‐crystal X‐ray methods. In both Ag 2 and Ag 3 , the structures of the macrocycles closely resemble that observed in the Ag I complex of 1 , where the metal atom adopts a three‐coordinate geometry with two agostic‐type interactions with the internal C–H units from the phenol or resorcinol rings.