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Solid-state one-way photoisomerisation of Z,E,Z-1,6-(4,4′-diphenyl)hexa-1,3,5-triene dicarboxylate examined using higher-order derivative spectra and powder XRD patterns
Photochemical & Photobiological Sciences ( IF 3.1 ) Pub Date : 2018-01-10 00:00:00 , DOI: 10.1039/c7pp00247e
Yoriko Sonoda 1, 2, 3, 4 , Midori Goto 3, 4, 5, 6, 7 , Kunihiro Ichimura 4, 8, 9, 10
Affiliation  

Higher order derivative spectra were applied at first to one-way ZEZ-to-EEE photoisomerisation of dimethyl ester (ZEZ-DPH1) of the titled compound in a methylcyclohexane solution. Many common crossing points emerged in UV-induced derivative-spectral changes to reveal the direct ZEZ-to-EEE photoisomerisation without the transient formation of an intermediate to suggest the bicycle-pedal mechanism. The solid-state photoisomerisation was subsequently monitored by tracing changes in the fourth-order derivatives of absorption spectra of a thin crystalline layer of ZEZ-DPH1 prepared by the drop-casting method, because the distortion of absorption spectra due to light scattering is cancelled. It was suggested that the solid-state photochemical event consists of three steps: fast ZEZ-to-EEE photoisomerisation, a subsequent slow ZEZ-to-EEE photoisomerisation and very slow disappearance of the EEE-isomer. Studies on powder XRD were also carried out for a drop-cast solid layer of ZEZ-DPH1 to disclose the coexistence of a crystal form other than the original one, and the former exhibited faster ZEZ-to-EEE photoisomerisation when compared with the original crystal form. The results revealed by XRD analysis are in line with those obtained by higher-order derivative spectra, confirming the solid-state one-way photoisomerisation to take place through the bicycle-pedal process.

中文翻译:

ZEZ -1,6-(4,4'-二苯基)六-1,3,5-三烯二羧酸酯的 固态单向光异构化,使用高阶导数光谱和粉末XRD图谱进行了研究

高阶导数光谱在首先施加到单向ZEZ -到- EEE二甲酯(光异构的ZEZ在甲基环己烷溶液,获得标题化合物的-DPH1)。在紫外线诱导的衍生物光谱变化中出现了许多常见的交叉点,以揭示直接的ZEZEEE的光异构化,而没有中间产物的瞬态形成来表明自行车踏板的机理。随后通过跟踪ZEZ薄晶体层吸收光谱的四阶导数变化来监控固态光异构化通过滴铸法制备的-DPH1,因为消除了由于光散射引起的吸收光谱的畸变。有人建议固态光化学事件包括三个步骤:快速ZEZ至- EEE光致异构化,随后缓慢ZEZ至- EEE光异构化和非常缓慢消失EEE异构体。研究粉末XRD也进行了用于下拉式铸造固体层ZEZ -DPH1披露比原来的一个其它的晶体形式的共存,前者表现出更快ZEZ -到- EEE与原始晶体形式相比,可进行光异构化。XRD分析揭示的结果与通过高阶导数光谱获得的结果一致,证实了固态单向光异构化将通过自行车踏板过程进行。
更新日期:2018-01-10
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