“…Azaacenes,the nitrogen-substituted analogues of acenes, have attracted much attention in the field of organic electronics as promising candidates for charge-transport materials because of their facile syntheses and higher chemical stability compared with larger acenes,s uch as pentacene. [1] Over the past decade,s everal research groups have reported the synthesis of novel azaacene derivatives by means of chemical modification of azaacene skeletons,f or example,b yi ntroducing functional groups [2,3] and/or extending the p-plane. [4] However,there have been few attempts to construct complicated structures by combining azaacene molecules,i ns pite of their potential for three-dimensional p-conjugated molecular bricolages.H erein, we report the shortest synthesis of double N-hetero [5]helicenes by adirect oxidative coupling of N-substituted pentacenes via their cruciform dimers to demonstrate the usefulness of these compounds as building blocks for novel three-dimensional (3D) p-systems (Scheme 1).…”