Laboratoire de Chimie Moléculaire et Spectroscopies Avancées (LCOSA), Ecole Européenne de Chimie, Polymères et Matériaux, CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 02, France.
Chemistry. 2010 Oct 18;16(39):11942-53. doi: 10.1002/chem.201001142.
Synthetic strategies have been devised that allow the rational design and isolation of highly coloured boron dipyrromethene (BODIPY) dyes that absorb across much of the visible region. Each dye has an aryl polycycle (usually pyrene or perylene) connected to the central BODIPY core through a conjugated tether at the 3,5-positions. Both mono- and difunctionalised derivatives are accessible, in certain cases containing both pyrene and perylene residues. For all new compounds, the photophysical properties have been recorded in solution at ambient temperature and in a glassy matrix at 77 K. The presence of the aryl polycycle(s) affects the absorption and emission maxima of the BODIPY nucleus, thereby confirming that these units are coupled electronically. Indeed, the band maxima and oscillator strengths depend on the conjugation length of the entire molecule, whereas there is no sign of fluorescence from the polycycle. As a consequence, the radiative rate constant tends to increase with each added appendage. The nature of the linkage (styryl, ethenyl, or ethynyl) also exerts an effect on the photophysical properties and, in particular, the absorption spectrum is perturbed in the region of the aryl polycycle. The perylene-containing BODIPY derivatives absorb over a wide spectral range and emit in the far-red region in almost quantitative yield. A notable exception to this generic behaviour is provided by the anthracenyl derivative, which exhibits charge-transfer absorption and emission spectra in weakly polar media at ambient temperature. Regular BODIPY-like behaviour is restored in a glassy matrix at 77 K. Overall, these new dyes represent an important addition to the range of strongly absorbing and emitting reagents that could be used as solar concentrators.
已经设计出了合成策略，可以合理设计和分离高度着色的硼二吡咯甲川（BODIPY）染料，这些染料在很大一部分可见区域内都有吸收。每个染料都有一个芳基多环（通常是芘或并五苯）通过 3,5-位的共轭键连接到中心的 BODIPY 核上。单官能和双官能化衍生物都可获得，在某些情况下，同时含有芘和并五苯残基。对于所有新化合物，在环境温度下的溶液中和在 77 K 的玻璃基质中都记录了光物理性质。芳基多环的存在会影响 BODIPY 核的吸收和发射最大值，从而证实这些单元在电子上是耦合的。实际上，带的最大值和振子强度取决于整个分子的共轭长度，而多环没有荧光的迹象。因此，辐射速率常数往往随着每个附加部分的增加而增加。键合的性质（苯乙烯基、乙烯基或乙炔基）也会对光物理性质产生影响，特别是吸收光谱在芳基多环的区域受到干扰。含并五苯的 BODIPY 衍生物在很宽的光谱范围内吸收，并在近定量产率下在远红区发射。这种普遍行为的一个显著例外是蒽衍生物，它在环境温度下的弱极性介质中表现出电荷转移吸收和发射光谱。在 77 K 的玻璃基质中，恢复了常规的 BODIPY 样行为。总的来说，这些新染料是对强烈吸收和发射试剂范围的重要补充，可作为太阳能集中器使用。
