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首页> 外文期刊>Crystal growth & design >Structural Transformations in Crystals Induced by Radiation and Pressure. Part 6. The Reactivity of Difluorocinnamic Acids under Ambient and High Pressures—Comparative Studies
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Structural Transformations in Crystals Induced by Radiation and Pressure. Part 6. The Reactivity of Difluorocinnamic Acids under Ambient and High Pressures—Comparative Studies

机译：辐射和压力致晶体的结构变换。 第六部分

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摘要

The influence of the molecular environment and the intramolecular features on the [2 + 2] photodimerization of 2,5-difluorocinnamic acid (1) and 3,5-difluorocinnamic acid (2) in crystals were analyzed. The crystal structures of (1) were determined at pressures of 0.1 MPa and 0.3 and 0.9 GPa before the [2 + 2] photodimerization as well as for several steps of the reaction. The determined structures revealed the influence of pressure on the reaction rate: the reaction was faster at 0.3 GPa than at 0.1 MPa, but there was not a significant difference between the rates at 0.3 and 0.9 GPa. For (2), the crystal structure was determined before the photochemical reaction, and the unit cell parameters were monitored along with the reaction progress at 0.1 MPa and 0.4 GPa, which showed higher reactivity of (2) at 0.4 GPa. Despite the similar orientations, distances between two neighboring monomers, and volumes of free space in the studied compounds, (2) reacted noticeably worse than (1). The differences in reactivity were rationalized in terms of the substituent effect of fluorine. The results were compared with those of our previous studies carried out for 2,6-difluorocinnamic acid (3).
机译：分析了分子环境和分子内特征对2,5-二氟乙酸（1）和3,5-二氟乙酸（2）的晶体中的[2 + 2]光二聚体的影响。 （1）的晶体结构在[2 + 2]光二聚体中的0.1MPa和0.3和0.9GPa的压力下确定，以及反应的几个步骤。确定的结构揭示了压力对反应速率的影响：反应在0.3GPa下比0.1MPa在0.1MPa下，但在0.3和0.9GPa的速率下没有显着差异。对于（2），在光化学反应之前测定晶体结构，并监测单位细胞参数随着0.1MPa和0.4GPa的反应进展，其显示在0.4GPa下的（2）的更高反应性。尽管取向相似，但是两个相邻单体之间的距离和所研究的化合物中的自由空间的体积，（2）明显比（1）更差。反应性的差异在氟的取代效应方面是合理化的。将结果与我们以前对2,6-二氟胞纤维酸（3）进行的研究的结果进行了比较。

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  • 来源
    《Crystal growth & design》 |2018年第3期|共9页
  • 作者

    Tomasz Galica; Julia B?kowicz; Krzysztof Konieczny; Ilona Turowska-Tyrk;

  • 作者单位

    Faculty of Chemistry Wroc?aw University of Science and Technology Wybrze?e Wyspiańskiego 27 50-370 Wroc?aw Poland;

    Faculty of Chemistry Wroc?aw University of Science and Technology Wybrze?e Wyspiańskiego 27 50-370 Wroc?aw Poland;

    Faculty of Chemistry Wroc?aw University of Science and Technology Wybrze?e Wyspiańskiego 27 50-370 Wroc?aw Poland;

    Faculty of Chemistry Wroc?aw University of Science and Technology Wybrze?e Wyspiańskiego 27 50-370 Wroc?aw Poland;

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  • 正文语种 eng
  • 中图分类 晶体学;
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