Polycyclic Aromatic Hydrocarbons Containing A Pyrrolopyridazine Core.
Polycyclic Aromatic Hydrocarbons Containing A Pyrrolopyridazine Core.
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DOI：
10.1002/cplu.201900031
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发表时间：
2019-02
期刊：
影响因子：
3.4
通讯作者：
Marcus Richter;Yubin Fu;E. Dmitrieva;J. Weigand;A. Popov;R. Berger;Junzhi Liu;Xinliang Feng
中科院分区：
文献类型：
--
作者：
Marcus Richter;Yubin Fu;E. Dmitrieva;J. Weigand;A. Popov;R. Berger;Junzhi Liu;Xinliang Feng
多环芳香甲亚胺叶立德（PAMYs）是一种自下而上合成含氮多环芳烃（N-PAH）的多功能结构单元。在这里，我们证明了PAMY和1，4-二苯基丁-2-炔-1，4-二酮之间的1，3-偶极环加成和随后与肼的缩合反应，这导致了独特的具有苯基取代的吡咯并哒嗪核的N-PAH（PP-1和PP-2）。通过NMR光谱和质谱验证了原始PP-1和叔丁基取代PP-2的分子结构。此外，通过X射线单晶分析明确地阐明了PP-2的结构。通过溶剂依赖的紫外-可见吸收光谱和荧光发射光谱以及循环伏安法研究了其光电性能。此外，密度泛函理论（DFT）计算表明，PP-1和PP-2表现出推拉行为。此外，在原位EPR/UV-Vis-NIR光谱电化学允许详细的洞察PP-2的自由基阳离子物种的光谱性质和自旋分布。
Polycyclic aromatic azomethine ylides (PAMYs) are versatile building blocks for the bottom-up construction of unprecedented nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Here, we demonstrate the 1,3-dipolar cycloaddition between PAMY and 1,4-diphenylbut-2-yne-1,4-dione and the subsequent condensation reaction with hydrazine, which led to unique N-PAHs with a phenyl-substituted pyrrolopyridazine core (PP-1 and PP-2). The molecular structures of pristine PP-1 and tert-butyl-substituted PP-2 were verified by NMR spectroscopy and mass spectrometry. Moreover, the structure of PP-2 was unambiguously elucidated by X-ray single crystal analysis. The optoelectronic properties were investigated by solvent-dependent UV-Vis absorption and fluorescence emission spectroscopy as well as cyclic voltammetry. Additionally, density functional theory (DFT) calculations showed that PP-1 and PP-2 exhibit push-pull behavior. Furthermore, in situ EPR/UV-Vis-NIR spectroelectrochemistry allowed the detailed insight into the spectroscopic properties and spin distribution of radical cation species of PP-2.