Abstract

Acenaphtho[1,2-k]fluoranthene (1) is synthesized via tandem cyclization during the dehydrofluorination of 1,4-di(1-naphthyl)-2,5-difluorobenzene (2) on activated γ-Al₂O₃. Presence of residual hydroxyl groups in alumina reduce the yield of target product 1 because of the side hydrolysis of fluoroarenes with the formation a product of partial cyclization, 9-(1-naphthyl)fluoranthen-8-ol (1b). The formation of negative ions (NI) of compounds 1 and 2 in the gas phase is studied by means of dissociative electron attachment (DEA) spectroscopy. Long-lived molecular NIs 1 and 2 are registered at the thermal energies of electrons, and patterns of their fragmentation are established. The adiabatic electron affinities of compounds 1 and 2 are estimated in the Arrhenius approximation and equal 1.17 ± 0.12 and 0.71 ± 0.07 eV, respectively, which agree with data from quantum chemical modeling at the level of the density functional theory (DFT). Electronic transitions for compounds 1 and 2 are studied via optical absorption and fluorescence spectroscopy. Fluorescence quantum yields are measured, and the resulting data are interpreted according to the time dependent DFT. The electrochemical properties of compounds 1, 1b, and 2 are studied via cyclic voltamperometry, and the levels of boundary molecular orbitals are estimated on the basis of their formal potentials of reduction and oxidation.

中文翻译：

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苊并[1,2-k]荧蒽：碳骨架转变在调节电子性能中的作用

摘要

苊并[1,2- k ]荧蒽( 1 )是在1,4-二(1-萘基)-2,5-二氟苯( 2 )在活化的γ-Al ₂ O ₃上脱氟化氢过程中通过串联环化合成的。氧化铝中残余羟基的存在降低了目标产物1的产率，因为氟代芳烃发生侧水解并形成部分环化产物9-(1-萘基)荧蒽-8-醇( 1b )。通过解离电子附着 (DEA) 光谱研究了化合物1和2在气相中负离子 (NI) 的形成。长寿命分子 NI 1和2记录了电子的热能，并建立了它们的碎片模式。化合物1和2的绝热电子亲和势根据阿伦尼乌斯近似估计，分别等于 1.17 ± 0.12 和 0.71 ± 0.07 eV，这与密度泛函理论 (DFT) 水平的量子化学模型数据一致。通过光学吸收和荧光光谱研究了化合物1和2的电子跃迁。测量荧光量子产率，并根据时间相关的 DFT 解释所得数据。化合物1、1b和2的电化学性质通过循环伏安法进行研究，并根据其形式的还原和氧化势来估计边界分子轨道的水平。