Inducing Open-shell Character in Porphyrins through Surface-assisted Phenalenyl π−Extension

Herein, we present a simple and straightforward method for the synthesis of phenalenyl-fused Pors (Por A0, PorA2 and PorA4) through readily available molecular precursors. While PorA0 was prepared by “wet” synthesis, the two- and four-fold phenalenyl-fused Por derivatives PorA2 and PorA4 were fabricated through a surface-assisted cyclodehydrogenation reaction from meso-2,6-dimethylphenyl(dmp) substituted precursors Por(dmp)2 and Por(dmp)4, respectively. In a systemat-ic way, we examined the structural and electronic properties of three surface-supported Pors.