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首页> 外文期刊>Chemistry: A European journal >Synthesis, characterization, molecular structure and theoretical studies of axially fluoro-substituted subazaporphyrins
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Synthesis, characterization, molecular structure and theoretical studies of axially fluoro-substituted subazaporphyrins

机译：轴向氟取代的亚氮杂卟啉的合成，表征，分子结构和理论研究

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摘要

A new and general synthetic method for the preparation of fluoro-substituted subazaporphyrins is reported that involves the treatment of the corresponding chloro- or aryloxy-substituted subazaporphyrins (SubAPs) with BF3 center dot OEt2. The strategy has been applied to both subphthalocyanines (SubPcs) and subporphyrazines (SubPzs). The yields were high for the latter, although low yields were obtained for the benzo derivatives. In contrast to the corresponding chloro derivatives, fluorosubazaporphyrins are quite robust towards hydrolysis. All of the new compounds were characterized by several spectroscopic techniques, which included H-1, C-13, F-19, N-15, and B-11 NMR spectroscopy, IR spectroscopy, UV/Vis spectrophotometry, and mass spectrometry (both high and low resolution). In addition, DFT calculations provided theoretical NMR spectroscopy values that are in good agreement with the experimental ones. The high dipole moments exhibited by the fluorosubazaporphyrins as a result of the presence of a fluorine atom in an axial position are responsible for the spontaneous and singular supramolecular aggregation of the macrocycles in the crystalline state. The molecular and crystal structures of two one-dimensional fluorine SubAPs, namely, a SubPc and a SubPz, are discussed. Molecules of the same class stack in alternating configurations along the c axis, which gives rise to columns that contain large numbers of monomers. SubPz 3c forms aggregates with the macrocycles arranged in a parallel fashion with the B-F bonds perfectly aligned within a column, whereas with SubPc 3b the neighboring columns cause a commensurate sinusoidal distortion along the columns in the c direction, which prevents the alignment of the B-F bonds. However, the most remarkable feature, common to both crystalline architectures, is the extremely short and unusual intermolecular F center dot center dot center dot N distances of the contiguous molecules, which are shorter than the sum of the corresponding van der Waals radii. Theoretical calculations have shown that these short distances can be explained by the existence of a cooperativity effect as the number of monomers included in the cluster increases.
机译：据报道，制备氟取代的亚氮杂卟啉的新的通用方法是用BF3中心点OEt2处理相应的氯或芳氧基取代的亚氮杂卟啉（SubAPs）。该策略已应用于亚酞菁（SubPcs）和亚卟啉（SubPzs）。后者的产率很高，尽管苯并衍生物的产率很低。与相应的氯衍生物相反，氟丁氮杂卟啉对水解非常有力。所有这些新化合物都通过几种光谱技术进行了表征，包括H-1，C-13，F-19，N-15和B-11 NMR光谱，IR光谱，UV / Vis分光光度法和质谱法（两者高和低分辨率）。此外，DFT计算提供了理论NMR光谱值，与实验值非常吻合。由于在轴向位置上存在氟原子，氟丁氮杂卟啉所表现出的高偶极矩是结晶态大环自发和奇异的超分子聚集的原因。讨论了两个一维氟SubAP，即SubPc和SubPz的分子和晶体结构。相同类别的分子沿c轴以交替构型堆叠，这导致包含大量单体的色谱柱。 SubPz 3c形成具有平行排列的大环的聚集体，其中BF键在列中完全对齐，而SubPc 3b相邻列在c方向上沿列引起相应的正弦形失真，从而阻止了BF键的对齐。然而，两种晶体结构共同的最显着特征是，连续分子的极短且不寻常的分子间F中心点中心点中心点N距离比相应的范德华半径之和短。理论计算表明，随着团簇中单体数量的增加，协同作用的存在可以解释这些短距离。

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