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Transmission Spectroscopy and Kinetics in Crystalline Solids Using Aqueous Nanocrystalline Suspensions: The Spiropyran-Merocyanine Photochromic System
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2017-01-18 00:00:00 , DOI: 10.1021/acs.cgd.6b01476 Vanessa M. Breslin 1 , Miguel A. Garcia-Garibay 1
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2017-01-18 00:00:00 , DOI: 10.1021/acs.cgd.6b01476 Vanessa M. Breslin 1 , Miguel A. Garcia-Garibay 1
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A comparison of the solution and solid state thermal decay kinetics of five photochromic spiropyrans with different N-alkyl groups (SP1–SP5) was carried out in acetonitrile and nanocrystalline suspensions at 298 K. The change in absorbance at ca. 550 nm was measured as a function of time for the merocyanine (MC) using transmission UV–vis spectroscopy. We found that the thermal decay kinetics are slower and follow a biexponential decay in the solid state compared to a faster, monoexponential decay that was measured in solution. We observed that, while the kinetic range measured in solution varies by a factor of 13, the decay kinetics in the solid state cover a range of ca. 150, indicating that crystal packing has an influence much greater than that of the effects of N-alkyl substitution. A fluorescence analysis of irradiated samples of SP1 in solution could be used to determine the formation of the MC species and its subsequent decay. By contrast, a similar analysis of nanocrystalline suspensions displayed changes as a function of time that are consistent with self-quenching.
中文翻译：
使用水性纳米晶体悬浮液的晶体固体的透射光谱和动力学：Spiropyran-花青光致变色系统
五个具有不同N烷基（SP1 – SP5）的光致变色螺吡喃的溶液和固态热衰变动力学的比较）在298 K的乙腈和纳米晶体悬浮液中进行。使用透射紫外可见光谱法测定了550 nm对时间的变化，从而测定了花青（MC）的时间。我们发现，与在溶液中测得的较快的单指数衰减相比，固态的热衰减动力学更慢并且遵循双指数衰减。我们观察到，虽然溶液中测得的动力学范围变化了13倍，但固态的衰变动力学却覆盖了约200范围。在图150中可以看出，表明晶体堆积的影响远大于N-烷基取代作用的影响。SP1辐照样品的荧光分析溶液中的溶液可用于确定MC物质的形成及其随后的衰变。相比之下，对纳米晶悬浮液的类似分析显示出随时间变化的变化与自淬火相一致。
更新日期：2017-01-18
中文翻译：
使用水性纳米晶体悬浮液的晶体固体的透射光谱和动力学：Spiropyran-花青光致变色系统
五个具有不同N烷基（SP1 – SP5）的光致变色螺吡喃的溶液和固态热衰变动力学的比较）在298 K的乙腈和纳米晶体悬浮液中进行。使用透射紫外可见光谱法测定了550 nm对时间的变化，从而测定了花青（MC）的时间。我们发现，与在溶液中测得的较快的单指数衰减相比，固态的热衰减动力学更慢并且遵循双指数衰减。我们观察到，虽然溶液中测得的动力学范围变化了13倍，但固态的衰变动力学却覆盖了约200范围。在图150中可以看出，表明晶体堆积的影响远大于N-烷基取代作用的影响。SP1辐照样品的荧光分析溶液中的溶液可用于确定MC物质的形成及其随后的衰变。相比之下，对纳米晶悬浮液的类似分析显示出随时间变化的变化与自淬火相一致。
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