A Poly(2,7‐anthrylene) with <i>peri</i> ‐Fused Porphyrin Edges

Abstract Anthracene has served as an important building block of conjugated polymers with the connecting positions playing a crucial role for the electronic structures. Herein, anthracene units have been coupled through their 2,7‐carbons to develop an unprecedented, conjugated polymer, namely, poly(2,7‐anthrylene) featuring additional peri ‐fused porphyrin edges. The synthesis starts from a 2,7‐dibromo‐9‐nickel(II) porphyrinyl‐anthracene as the pivotal precursor. Polymerization is achieved by an AA‐type Yamamoto coupling, followed by a polymer‐analogous oxidative cyclodehydrogenation to obtain a peri ‐fusion between porphyrin and anthracene moieties. Although further cyclodehydrogenation between the repeating units cannot be achieved in solution, the thermal treatment of the precursor polymer derived from 2,7‐dibromo‐9‐porphyrinyl‐anthracene on a metal surface realizes the full cyclodehydrogenation. The difference between solution and on‐surface reactivity can be rationalized by the larger dihedral angle between repeat units in solution, which is reduced under the pronounced interaction with the metal surface. The peri ‐fusion in the title polymer gives rise to a narrow electronic band gap optical absorptions extending far into the near‐infrared region. Oligomeric models are synthesized as well to support the analyses of the electronic and photophysical properties.