Anthracenylporphyrins

Abstract

We report the synthesis and characterization of meso-anthracenylporphyrins with zinc and nickel metal centers. A variety of novel aryl and alkyl meso-substituted anthracenylporphyrins were synthesized via step-wise Suzuki cross-coupling reactions using anthracenyl boronates. This method was compared to standard syntheses based on condensation reactions to yield anthracenylporphyrins of the A 2 B 2 -and A 3 B-type. The work was complemented by the synthesis of a number of the functionalized anthracene derivatives via Suzuki couplings. Selected systems were subjected to single-crystal X-ray analysis which revealed an unusual close packing for nickel(II) anthracenylporphyrins.

5,15‐A2B2‐ and 5,15‐A2BC‐Type Porphyrins with Donor and Acceptor Groups for Use in Nonlinear Optics and Photodynamic Therapy

“…As shown in Scheme porphyrins with 1‐naphthyl ( 3 and 5 ) and 9‐phenanthrenyl ( 4 ) substituents were obtained in 18–31 % yield. Attempts to prepare the related bisanthracenylporphyrin gave only the monosubstituted scrambling product 6 in low yield 14. For comparative purposes we also included the well known 3‐methoxy derivative 7 in our investigations 15…”

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies

“… Locos et al. found that the use of AsPh 3 as a ligand with PdCl 2 (PPh 3 ) 2 improved the yield of the reaction between dibromoporphyrin 52.1Ni and 9-borylanthracene to 78% . In this case, Ni­(II) complexes afforded superior product yields to free-base and Zn­(II) derivatives.…”

[5,15-Bis(2-methylpropyl)porphyrinato]nickel(II)

“…For the structural analysis of -aggregates, see: Scheidt & Lee (1987). For Ni(II) porphyrin structures, see: Song et al (1996Song et al ( , 1998; Davis et al (2010); Jentzen et al (1996); ; Senge et al (2000;. For the preparation, see: Wiehe et al (2005).…”

“…meso-Alkylporphyrins are increasingly used in porphyrin chemistry, but their structural chemistry is less well established . The compound is another example for the expanding body of Ni(II) porphyrins with a planar macrocycle (Davis et al, 2010;Jentzen et al, 1996;. In the crystal this allows the formation of πaggregates which are characterized by a mean plane separation of 3.36 (2) Å, a center-to-center distance of 4.88 (2) Å, a slip angle of 133.5 (1) ° which, according to the classification given by Scheidt & Lee (1987), results in a lateral shift of the metal centers of 3.54 (2) Å.…”