N‐Fusion Reaction Sequence of Heptaphyrin(1.1.1.1.1.1.1): Singly, Doubly, and Quadruply N‐Fused Heptaphyrins

meso ‐Heptakis(pentafluorophenyl) heptaphyrin(1.1.1.1.1.1.1) ( 1 ) was prepared by a stepwise route in 39 % yield and its unique N‐fusion reaction (NFR) sequence has been revealed; this reaction leads to singly‐, doubly‐, and quadruply N‐fused heptaphyrins ( 4 , 5 , and 6 ) in good yields. These transformations are facilitated by the inherent conformational distortion of 1 as well as the distorted, folded conformations of N‐fused heptaphyrins 4 and 5 . The proximate arrangement of the three pyrrole units in 6 allowed for the formation of the tripyrrolylboron(III) complexes 7 , 8 , and 9 with unique coordination features. Molecules 1 , 5 , and 9 were structurally characterized by X‐ray crystallography. In addition, the boron complexes 7 , 8 , and 9 displayed weak but distinct fluorescence in the near infrared region.