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The preparation of large azaacenes is very important because of their great potential in organic electronics. In this report, we successfully synthesized and fully characterized two stable pyrene‐fused large azaacenes: octaazadecacene and tetraazaoctacene through employing a relatively moderate aromatic unit pyrene as imbedded species in the backbone of azaacenes to ensure large conjugation and stability. The photoelectrochemical (PEC) studies indicate that both azaacenes display n‐type semiconductor behavior.  相似文献   
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