Departamento de Sistemas de Baja Dimensionalidad, Superficies y Materia Condensada, Instituto de Química-Física Rocasolano, CSIC, Madrid, Spain.
Chemphyschem. 2012 Dec 7;13(17):3923-31. doi: 10.1002/cphc.201200587. Epub 2012 Sep 11.
Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red-emitting boron-dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single- and double-substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non-radiative deactivation processes can be softened by decreasing the electron-donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red-edge BODIPYs with highly efficient and photostable laser emission.
在此，我们提出了一种新型的发射红光的硼二吡咯甲烷（BODIPY）的合成路线，以及其光物理、电化学和激光性质。这种功能基团沿着发色团的主轴线添加，导致单取代和双取代衍生物的形成。借助光物理和电化学性质以及量子力学模拟，详细研究了染料结构与激光性质之间的关系。母体染料的不对称取代会导致电荷分布不均匀，从而导致荧光能力的整体丧失，主要发生在极性介质中。这种非辐射去活化过程可以通过降低取代基的给电子能力来减轻，甚至可以通过对称取代来避免。因此，将苯乙炔基团接枝到茚并核心的纵轴上是开发具有高效和稳定激光发射的红色边缘 BODIPY 的有效策略。
