The Reasons for Different Kinetics of the Norrish-Yang Reaction in Crystals. Structural and Spectroscopic Studies

Konieczny Krzysztof A.; Szczurek Anna; Bqkowicz Julia; Siedlecka Renata; Ciesielski Arkadiusz; Cyranski Michal K.; Turowska-Tyrk Ilona

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The Reasons for Different Kinetics of the Norrish-Yang Reaction in Crystals. Structural and Spectroscopic Studies

机译：晶体晶胞反应不同动力学的原因。结构和光谱研究

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The kinetics of the photochemical Norrish-Yang reaction in single crystals was studied using the example of 1,3,5,7-tetraazatricyclo [3.3.1.13,7] decane 4-(2,4,6-triisopropylbenzoyl)-benzoate by X-ray diffraction and Raman spectroscopy. The reaction in the studied compound proceeds in two stages described by the Johnson-Mehl-Avrami-Kolmogorov model. In the first stage the reaction progresses homogeneously at a constant rate, but for the second mode, which started at ca. 50% conversion, the reaction progresses with autoinhibition. The reasons for this autoinhibition are (i) the changes in the geometry of the reaction center during the second stage, which were not observed in the first stage, (ii) the C-H center dot center dot center dot pi interactions, which become stronger along with the reaction progress, and (iii) the change in character of the carboxylate group toward the carboxylic-like group. The Norrish-Yang reaction also proceeds in crystals at 0.2 GPa, as stated on the grounds of the characteristic changes in the unit cell parameters along with UV irradiation.

机译：使用X的1,3,5,7-四唑酸酐[3.3.1.1.13,7]癸烷4-（2,4,6-三异丙基苯甲酰苯甲酰基）的实施例研究了单晶中的光化学Norrish-yang反应的动力学 - 射线衍射和拉曼光谱。所研究的化合物中的反应在约翰逊-Mehl-Avrami-Kolmogorov模型描述的两个阶段进行。在第一阶段，反应以恒定速率均匀进展，但是对于在CA开始的第二种模式。转化50％，反应进展自动化。这种自动抑制的原因是（i）在第二阶段在第一阶段未观察到的反应中心的几何形状的变化，（ii）CH中心点中心点中心点PI相互作用，变得更强随着反应进展，（iii）羧酸盐基团的变化朝向羧酸样基团的变化。 Norrish-yang反应还在0.2GPa的晶体中进行，如在单位细胞参数的特征变化以及紫外线照射的基础上。

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《Crystal growth & design》 |2020年第8期|共11页
作者
Konieczny Krzysztof A.; Szczurek Anna; Bqkowicz Julia; Siedlecka Renata; Ciesielski Arkadiusz; Cyranski Michal K.; Turowska-Tyrk Ilona;
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作者单位

Wroclaw Univ Sci &

Technol Adv Mat Engn &

Modelling Grp PL-50370 Wroclaw Poland;

Wroclaw Univ Sci &

Technol Dept Mech Mat Sci &

Engn PL-50370 Wroclaw Poland;

Wroclaw Univ Sci &

Technol Adv Mat Engn &

Modelling Grp PL-50370 Wroclaw Poland;

Wroclaw Univ Sci &

Technol Dept Organ Chem PL-50370 Wroclaw Poland;

Univ Warsaw Sect Theoret Chem &

Crystallog Pasteura 1 PL-02093 Warsaw Poland;

Univ Warsaw Sect Theoret Chem &

Crystallog Pasteura 1 PL-02093 Warsaw Poland;

Wroclaw Univ Sci &

Technol Adv Mat Engn &

Modelling Grp PL-50370 Wroclaw Poland;

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正文语种 eng
中图分类晶体学;
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The Reasons for Different Kinetics of the Norrish-Yang Reaction in Crystals. Structural and Spectroscopic Studies

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