Synthesis of a 4,9-Didodecyl Angular-Shaped Naphthodiselenophene Building Block To Achieve High-Mobility Transistors

A new tetracyclic 4,9-dialkyl angular-shaped naphthodiselenophene (4,9-α-aNDS) was designed and synthesized. The naphthalene core in 4,9-α-aNDS is formed by the DBU-induced 6π-cyclization of an (E)-1,2-bis­(3-(tetradec-1-yn-1-yl)­selenophen-2-yl)­ethene intermediate followed by the second PtCl2-catalyzed benzannulation. This synthetic protocol allows for incorporating two dodecyl groups regiospecifically at 4,9-positions of the resulting α-aNDS. An ordered supramolecular self-assembly formed via noncovalent selenium–selenium interactions with a short contact of 3.5 Å was observed in the single-crystal structure of 4,9-α-aNDS. The distannylated α-aNDS building block was copolymerized with Br-DTFBT and Br-DPP acceptors by Stille cross coupling to form two new donor–acceptor polymers PαNDSDTFBT and PαNDSDPP, respectively. The bottom-gate/top-contact organic field-effect devices using the PαNDSDTFBT and PαNDSDPP semiconductors accomplished superior hole mobility of 3.77 and 2.17 cm2 V–1 s–1, respectively, which are among the highest mobilities reported to date.本研究设计并合成了一种新型四环4,9-二烷基角型萘并二硒吩（4,9-α-aNDS）。4,9-α-aNDS中的萘环核心，首先通过DBU诱导的(E)-1,2-双(3-(十四碳-1-炔-1-基)硒吩-2-基)乙烯中间体发生6π环化反应，再经PtCl₂催化的苯环化反应构建得到。该合成路线可在所得α-aNDS的4,9位区域选择性地引入两个十二烷基基团。在4,9-α-aNDS的单晶结构中，观察到通过3.5 Å的短程非共价硒-硒相互作用形成的有序超分子自组装结构。将二锡烷基化的α-aNDS构筑单元与Br-DTFBT、Br-DPP受体通过施蒂勒交叉偶联反应分别共聚，得到两种新型给体-受体聚合物PαNDSDTFBT与PαNDSDPP。以PαNDSDTFBT与PαNDSDPP作为半导体层的底栅顶接触型有机场效应器件，分别实现了3.77 cm²·V⁻¹·s⁻¹与2.17 cm²·V⁻¹·s⁻¹的优异空穴迁移率，这两项数值均为目前已报道的最高迁移率之一。