Müller Matthias, Beglaryan Stella S, Koser Silke, Hahn Sebastian, Tverskoy Olena, Rominger Frank, Bunz Uwe H F
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry. 2017 May 23;23(29):7066-7073. doi: 10.1002/chem.201700421. Epub 2017 May 2.
Herein, we report the synthesis, spectroscopic, and structural properties of novel 2,3-dicyano-substituted azaacenes containing three to six annelated rings as a framework. The targets were prepared by Pd-catalyzed coupling of diamino-bis(tri-isopropylsilylethynyl)benzene, -naphthalene, and -anthracene with either 4,5-dibromophthalonitrile or 6,7-dibromonaphthalene-2,3-dicarbonitrile into the respective N,N'-dihydrodiazaacenes. Oxidation with MnO or PbO furnishes the dicyano-substituted diazaacenes in reasonable to good yields. An exception is the diazahexacene, where the N,N'-dihydrodiazaacene is difficult to oxidize. Most of the targets could be crystallized and pack in isolated pairs, stacks, and brick-wall motifs. The n-type behavior of these molecules was illustrated in a proof-of-concept organic field-effect transistor, showing mobilities up to 7×10 cm V s .
在此，我们报道了以含三至六个稠合环的新型2,3 - 二氰基取代氮杂并苯为骨架的合成、光谱及结构性质。通过钯催化二氨基 - 双（三异丙基甲硅烷基乙炔基）苯、萘和蒽与4,5 - 二溴邻苯二甲腈或6,7 - 二溴萘 - 2,3 - 二甲腈偶联制备目标化合物，得到相应的N,N'-二氢二氮杂并苯。用MnO或PbO氧化以合理至良好的产率得到二氰基取代的二氮杂并苯。二氮杂六并苯是个例外，其N,N'-二氢二氮杂并苯难以氧化。大多数目标化合物能够结晶，并以孤立对、堆叠和砖墙 motif 形式堆积。这些分子的n型行为在概念验证有机场效应晶体管中得到说明，显示出高达7×10⁻⁴ cm² V⁻¹ s⁻¹ 的迁移率。
