Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Japan Society for the Promotion of Science (JSPS/PD) , Ichibancho, Chiyoda-ku, Tokyo 102-8471, Japan.
ACS Appl Mater Interfaces. 2016 Mar 23;8(11):7522-8. doi: 10.1021/acsami.5b11988. Epub 2016 Mar 8.
Two types of +3-charged subporphyrin derivatives with m- and p-methylpyridinium as the meso-aryl substituents were designed and synthesized. Their photophysical properties with and without anionic saponite clay were investigated. These cationic subporphyrins were suitably designed for adsorption on the saponite nanosheet surface with their photoactivity. Absorption and emission spectra of these subporphyrin-saponite complexes exhibited strong bathochromic shifts due to the flattening of the molecules on the nanosheet. This behavior was observed as drastic visual changes in their luminescence colors. Additionally, aggregation behaviors were not observed in the saponite complexes even at high dye loading levels for both subporphyrins. Moreover, under such condition, their fluorescence properties on the saponite surface were not only maintained but also enhanced without unexpected deactivations despite the dye molecules are densely introduced on the solid surface. These findings are beneficial for applications of the dye-clay complexes to photofunctional materials such as strongly luminescent materials, highly sensitive clay sensors and artificial photosynthesis systems.
两种类型的带正三价电荷的次卟啉衍生物，其meso-芳基取代基为 m-和 p-甲基吡啶鎓，被设计并合成。研究了它们在有无阴离子皂石粘土的情况下的光物理性质。这些阳离子次卟啉被适当设计用于在纳米片表面上吸附，从而具有光活性。这些次卟啉-皂石配合物的吸收和发射光谱由于分子在纳米片上的扁平化而表现出强烈的红移。这种行为表现为它们发光颜色的剧烈视觉变化。此外，即使在两种次卟啉的高染料负载水平下，在皂石配合物中也没有观察到聚集行为。此外，在这种情况下，尽管染料分子在固体表面上密集引入，但它们在皂石表面上的荧光性质不仅得以保持，而且在没有意外失活的情况下得到增强。这些发现有利于将染料-粘土配合物应用于光功能材料，如强发光材料、高灵敏度粘土传感器和人工光合作用系统。
