Several hexaazatrinaphthylene derivatives and a tris(thieno)hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and pi-stacking with an average spacing between adjacent molecular planes of 3.18 A. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range -2.65 to -4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoromethyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoromethyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting pi-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials.

中文翻译：

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六氮杂萘并萘衍生物的合成，电离势和电子亲和力。

通过适当的二胺与六酮环己烷的反应，已经合成了几种六氮杂萘并萘衍生物和三（硫杂）六氮杂苯并菲衍生物。通过X射线衍射测定了2,3,8,9,14,15-六氯-5,6,11,12,17,18-六氮杂萘并萘的晶体结构; 这表明分子结构与密度泛函理论（DFT）计算和pi堆积所预测的分子结构非常吻合，相邻分子平面之间的平均间距为3.18A。已使用紫外光电子能谱法测定了固态电离电势，固态电子亲和力在5.99至7.76 eV的范围内变化，而使用逆光电子能谱测量的固态电子亲和力在-2.65至-4.59 eV的范围内变化。最容易还原的例子是被双（三氟甲基）苯基取代的三（硫代）六氮杂三苯并苯；DFT计算表明，高度放热的电子亲和力是由于六氮杂萘并萘的最外亚苯基环被噻吩基取代和吸电子的双（三氟甲基）苯基的存在。通过DFT计算获得的相当高的放热电子亲和力，采用π堆积结构的潜力以及较低的分子内重组能表明这些分子中的某些可能是有用的电子传输材料。DFT计算表明，高度放热的电子亲和力是由于六氮杂萘并萘的最外亚苯基环被噻吩基取代和吸电子的双（三氟甲基）苯基的存在。通过DFT计算获得的相当高的放热电子亲和力，采用π堆积结构的潜力以及较低的分子内重组能表明这些分子中的某些可能是有用的电子传输材料。DFT计算表明，高度放热的电子亲和力是由于六氮杂萘并萘的最外亚苯基环被噻吩基取代和吸电子的双（三氟甲基）苯基的存在。通过DFT计算获得的相当高的放热电子亲和力，采用π堆积结构的潜力以及较低的分子内重组能表明这些分子中的某些可能是有用的电子传输材料。