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首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >Electrooptic Kerr effect of porphyrin H-aggregates in polymer films: Polymer specific spectral blue shift
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Electrooptic Kerr effect of porphyrin H-aggregates in polymer films: Polymer specific spectral blue shift

机译：聚合物薄膜中卟啉H聚集体的电光Kerr效应：聚合物特定光谱的蓝移

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摘要

J- and H-aggregates of porphyrin molecules (TPPS4) in spin-coated polymer films have been studied by electroabsorption and circular dichroism (CD) spectroscopy. A spectral blue shift of the H-band due to the electrooptic Kerr effect was observed for the first time. This occurs only for a polyvinylpyrrolidone (PVP) film, with negligibly small spectral shift observed in polyvinyl alcohol (PVA), polyvinyl sulfate (PVS), and polyacrylic acid (PAA) films, in contrast to the red shift of the J-band which is commonly observed for any host polymers. Accordingly, the CD activity in both of J- and H-bands is more enhanced in PVP films than in PVA films. The mechanism of the blue and red shifts of the respective H- and J-bands is discussed by invoking a helical structure in micro-aggregates, which is compatible with the CD spectra, based on the molecular rearrangement model. It is proved that blue-and red-shifts occur evenly to cancel each other in the H-band if a simple helical structure is assumed, in good agreement with no spectral shifts in the H-band in PVA, PVS, and PAA films. (C) 2016 Elsevier B.V. All rights reserved.
机译：通过电吸收和圆二色性（CD）光谱研究了旋涂聚合物薄膜中卟啉分子（TPPS4）的J和H聚集体。首次观察到由于电光克尔效应导致的H波段光谱蓝移。这种现象仅发生在聚乙烯吡咯烷酮（PVP）膜上，而在聚乙烯醇（PVA），聚硫酸乙烯（PVS）和聚丙烯酸（PAA）膜中观察到的光谱位移可忽略不计，而J波段的红移与通常观察到任何主体聚合物。因此，与PVA膜相比，PVP膜在J带和H带中的CD活性都增强。基于分子重排模型，通过调用微聚集体中的螺旋结构来讨论相应H谱带和J谱带的蓝移和红移的机理，该结构与CD光谱兼容。事实证明，如果假设一个简单的螺旋结构，则蓝移和红移会在H带中均匀发生，从而相互抵消，这与PVA，PVS和PAA薄膜的H带中没有光谱偏移完全吻合。 （C）2016 Elsevier B.V.保留所有权利。

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