Bliksted Roug Pedersen Viktor, Granhøj Jeppe, Erbs Hillers-Bendtsen Andreas, Kadziola Anders, Mikkelsen Kurt V, Brøndsted Nielsen Mogens
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
Chemistry. 2021 Jun 4;27(32):8315-8324. doi: 10.1002/chem.202100984. Epub 2021 May 19.
Polycyclic aromatic hydrocarbons (PAHs) have found strong interest for their electronic properties and as model systems for graphene. While PAHs have been studied intensively as single units, here PAHs were constructed in ladder-type arrangements using cross-conjugated fulvalene and dithiafulvalene motifs as connecting units and moving forward a convenient synthetic approach for dimerizing (thio)ketones into olefins by the action of Lawesson's reagent. Some of the PAHs can also be regarded as "super-extended" tetrathiafulvalenes (TTFs) with some of the largest cores ever explored, being multi-redox systems that exhibit both reversible oxidations and reductions. Concomitant absorption redshifts were observed when expanding the ladder-type structures from one to two to three indenofluorene units, and optical and electrochemical HOMO-LUMO gaps were found to correlate linearly. Various conformations (and solid-state packing arrangements) were studied by X-ray crystallography and computations.
多环芳烃（PAHs）因其电子性质以及作为石墨烯的模型体系而备受关注。虽然PAHs作为单个单元已被深入研究，但在此研究中，使用交叉共轭富瓦烯和二硫代富瓦烯基序作为连接单元，以阶梯型排列构建了PAHs，并推进了一种通过Lawesson试剂将（硫）酮二聚化为烯烃的便捷合成方法。一些PAHs还可被视为具有有史以来探索的一些最大核心的“超扩展”四硫富瓦烯（TTFs），它们是既表现出可逆氧化又表现出可逆还原的多氧化还原体系。当将阶梯型结构从一个茚并芴单元扩展到两个再到三个茚并芴单元时，观察到伴随的吸收红移，并且发现光学和电化学HOMO-LUMO能隙呈线性相关。通过X射线晶体学和计算研究了各种构象（以及固态堆积排列）。
