Domino Insertion-Coupling Synthesis of Solid-State Luminescent Propynylidene Indolones.
Domino Insertion-Coupling Synthesis of Solid-State Luminescent Propynylidene Indolones.
复制标题
DOI：
10.1002/chem.201802237
复制
发表时间：
2018-09
期刊：
影响因子：
--
通讯作者：
Jan Schoenhaber;D. M. D'Souza;Tobias Glißmann;B. Mayer;C. Janiak;F. Rominger;W. Frank;T. Müller
中科院分区：
文献类型：
--
作者：
Jan Schoenhaber;D. M. D'Souza;Tobias Glißmann;B. Mayer;C. Janiak;F. Rominger;W. Frank;T. Müller
3-芳基亚丙基吲哚酮类化合物是三组分连续合成各种具有特殊发光特性的吲哚类发色团的关键中间体，通过多米诺插入偶联合成，以中等至优异的产率合成了具有电子多样性取代模式的化合物。标题化合物以100：0至0：100的E/Z比形成。除了通过NMR光谱和X-射线结构分析进行结构解析之外，还采用DFT计算来合理化所观察到的立体选择性。3-芳基亚丙基吲哚酮的光物理性质的特征在于强烈的，可调的，固态发射的N-取代的衍生物作为定量的滴铸膜。通过DFT和TD-DFT计算证实了电子基态结构，表明梯度校正的交换和相关PBE（Perdew-Burke-Ernzerhof）泛函可以成功地用于正确地再现所观察到的mercury衍生物的吸收特性。巨大的斯托克斯位移强烈依赖于电子替代模式支持的Hammett-Taft相关。
The compound class of 3-arylpropynylidene indolones, key intermediates in consecutive three-component syntheses of various indole-based chromophores with peculiar emission characteristics, are readily synthesized by a domino insertion-coupling synthesis with an electronically diverse substitution pattern in moderate to excellent yields. The title compounds are formed in E/Z-ratios from 100:0 to 0:100. Besides structure elucidation by NMR-spectroscopy and X-ray structure analysis, DFT calculations have been employed to rationalize the observed stereoselectivity. The photophysical properties of 3-arylpropynylidene indolones are characterized by intense, tunable, solid-state emission of N-substituted derivatives as quantified for drop-cast films. The electronic ground state structure was corroborated by DFT and TD-DFT calculations, showing that gradient-corrected exchange and correlation PBE (Perdew-Burke-Ernzerhof) functionals can be successfully employed to correctly reproduce the observed absorption characteristics of merocyanine derivatives. The huge Stokes shifts strongly depend on the electronic substitution pattern as supported by Hammett-Taft correlations.