Rosenberg Martin, Santella Marco, Bogh Sidsel A, Muñoz Alberto Viñas, Andersen Helene O B, Hammerich Ole, Bora Ilkay, Lincke Kasper, Laursen Bo W
Nano-Science Center and Department of Chemistry , University of Copenhagen , Universitetsparken 5 , Copenhagen 2100 , Denmark.
J Org Chem. 2019 Mar 1;84(5):2556-2567. doi: 10.1021/acs.joc.8b02978. Epub 2019 Feb 19.
The very limited class of fluorophores, with a long fluorescence lifetime (>10 ns) and fluorescence beyond 550 nm, has been expanded with two benzo-fused triangulenium derivatives and two cationic [5]-helicene salts. The syntheses of the benzo-bridged dioxa- and diazatriangulenium derivatives (BDOTA and BDATA, respectively) required two different synthetic approaches, which reflect the structural and physiochemical impact on the reactivity of [5]-helicenium precursors. Spectroscopic investigations show that the introduction of the benzo bridge into the triangulenium chromophore significantly redshifts the absorption and emission while maintaining fluorescence lifetimes above 10 ns. The combination of a high quantum yield, long fluorescence lifetime, and emission above 600 nm is possible only if the structural aspects of the triangulenium framework are perfectly harmonized to secure a low rate of nonradiative deactivation. The new benzo bridge may be a general motif to obtain red-shifted derivatives of other dye classes.
具有长荧光寿命（>10纳秒）且荧光波长超过550纳米的荧光团种类非常有限，现在通过两种苯并稠合的三角烯衍生物和两种阳离子[5] - 螺旋烯盐得以扩展。苯并桥连的二氧杂和二氮杂三角烯衍生物（分别为BDOTA和BDATA）的合成需要两种不同的合成方法，这反映了[5] - 螺旋烯前体的结构和物理化学性质对反应性的影响。光谱研究表明，将苯并桥引入三角烯发色团会使吸收和发射显著红移，同时保持荧光寿命高于10纳秒。只有当三角烯骨架的结构方面完美协调以确保低非辐射失活速率时，才有可能实现高量子产率、长荧光寿命和600纳米以上发射的组合。新的苯并桥可能是获得其他染料类红移衍生物的通用基序。
