Tris(4-cyanophenyl)amine: Simple synthesis via self-assembly; Strong fluorescence in solution, nano/microcrystals, and solid
Tris(4-cyanophenyl)amine: Simple synthesis via self-assembly; Strong fluorescence in solution, nano/microcrystals, and solid
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DOI：
10.1002/adfm.200600931
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发表时间：
2007-09-03
影响因子：
19
通讯作者：
Radhakrishnan, T. P.
中科院分区：
文献类型：
--
作者：
Patra, Abhijit;Anthony, S. Philip;Radhakrishnan, T. P.
三重对称分子，三（4-氰基苯基）胺（TCPA）的合成从4-氟氰基苯与碳酸钾在二甲基亚砜中处理;没有任何胺试剂的反应的发生表明一个新的自组装过程的参与。再沉淀策略提供了稳定的胶体，其含有高度单分散的纳米/微晶，具有明确的立方形态和可从250至500 nm调节的尺寸。溶液，胶体和固体状态的TCPA表现出强烈的蓝色荧光，胶体显示出双发射与一个异常小的斯托克斯位移。计算研究进行了分子和超分子组装来自晶体结构。再加上详细的光谱研究，他们表明，在胶体和固体状态的发射可以归因于能量水平产生的凝聚相和它们之间的能量级联中的不同聚集基序内的分子间相互作用。计算还揭示了分子晶体中存在的协同相互作用有助于其高热稳定性。TCPA同时在溶液、纳米/微晶和固态中表现出的强发光使其成为具有潜在实用性的新型分子材料;它导致了对描述在不同物理状态下观察到的现象的潜在机制的探索。
The threefold symmetric molecule, tris(4-cyanophenyl)amine (TCPA) is synthesized from 4-fluorocyanobenzene by treatment with potassium carbonate in dimethylsulfoxide; the occurrence of the reaction without any amine reagent suggests the involvement of a novel self-assembly process. A reprecipitation strategy provides stable colloids containing highly monodisperse nano/microcrystals with well-defined cubic morphology and sizes tunable from 250 to 500 nm. The solution, colloid, and solid states of TCPA exhibit strong blue fluorescence; the colloid shows dual emission with an unusually small Stokes shift. Computational investigations are carried out on the molecule and supramolecular assemblies derived from the crystal structure. Coupled with detailed spectroscopic studies, they show that the emission in the colloidal and solid states can be attributed to energy levels resulting from the intermolecular interactions within different aggregation motifs in the condensed phase and energy cascades between them. The computations also reveal the presence of cooperative interactions in the molecular crystal contributing to its high thermal stability. The strong light emission exhibited by TCPA, concurrently in the solution, nano/microcrystal, and solid states establishes it as a novel molecular material of potential practical utility; it has led to the exploration of the underlying mechanism that describes the phenomena observed in the different physical states.