苝酰亚胺在L型沸石一维通道中的相互作用

Michael Busby, A. Devaux, C. Blum, V. Subramaniam, G. Calzaferri, L. Cola
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引用次数: 48

摘要

在真空条件下,将三种端取代基不同的苝染料插入到L型沸石(ZL)纳米通道中,通过气相吸附制备了超分子组织的主客体体系。末端取代基可以控制通道中分子的核间距离。所研究的三种苝染料在稀释溶液中具有非常相似的吸收和荧光光谱,以及荧光寿命~ 4 ns。采用长度在1500 ~ 3000 nm,直径在1000 nm左右的大ZL晶体和长度和直径在30 nm左右的纳米级NZL晶体作为寄主。研究了不同的载荷。以悬浮液的形式分析了材料在折射率匹配溶剂(甲苯或苯甲酸乙酯)中的光物理性质;在玻璃容器中作为散装材料;并采用时间、空间、光谱分辨单晶荧光显微光谱技术。如果苝衍生物的结构允许在线排列的电子跃迁矩之间的短距离,则插入的染料可以形成j聚集体。具有取代基的分子没有发现j偶联,取代基使分子之间的距离更远。一维通道中对齐和稳定的j聚集体为制备光学器件提供了新的选择,其中纳米到微米尺度上的相干激子离域可能导致高效的光子线。激子耦合可以通过改变分子尾基来控制。
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Interactions of Perylene Bisimide in the One Dimensional Channels of Zeolite L
Supramolecularly organized host guest systems have been prepared by inserting three perylene dyes with differing end substituents into the nanosized channels of zeolite L (ZL) by gas-phase adsorption under vacuum conditions. The end substituents allowed controlling the core-to-core distances of the molecules in the channels. The three perylene dyes investigated have very similar absorption and fluorescence spectra in diluted solutions, as well as fluorescence lifetimes ∼ 4 ns. Large ZL crystals in the size range of 1500−3000 nm in length and about 1000 nm in diameter as well as nanosized NZL crystals of about 30 nm in length and diameter were used as hosts. Different loadings have been investigated. The photophysical properties of the materials were analyzed as suspensions in refractive index matching solvents, such as toluene or ethyl benzoic acid ester; as bulk materials in glass ampules; and by means of time-, space-, and spectrally resolved single-crystal fluorescence microspectrocopy techniques. The inserted dyes can form J-aggregates if the structure of the perylene derivative allows for short distances between the electronic transition moments in an in-line arrangement. J-coupling was not seen for the molecules with substituents that keep them further apart. Aligned and stabilized J-aggregates in one-dimensional channels provide new options for preparing optical devices, where coherent exciton delocalization over nanometer-to-micrometer scales may result in efficient photonic wires. The exciton coupling can be controlled by varying the molecular tail groups.
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