期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 12, 期 8, 页码 2358-2370出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200500948
关键词
boranes; charge transfer; fluorescence spectroscopy; solvatochromism; symmetry breaking; UV/Vis spectroscopy
We synthesized a series of amino substituted triarylboranes (TABs) 1-3 by copper((I))-catalyzed cross-coupling reactions. The title compounds were investigated by means of cyclic voltammetry (CV) and UV-visible absorption and fluorescence spectroscopy. Electrochemical oxidation of tris(4-carbazolyl-2,6-dimethylphenyl)-borane (3) leads to the formation of an electroactive polymer film on the electrode surface. The charge-transfer (CT) absorption band of all three TABs shows a pronounced negative solvato-chromism, while the emission is positively solvatochromic. By combining Jortner's theory, AMI computations, and electrooptical absorption measurements (EOAM), this unexpected behavior was shown to be due to a dipole inversion upon S-0 -> S-1 excitation. Furthermore, polarized steady-state fluorescence spectroscopy and EOAM prove that the ground-state geometry of 3 is of lower symmetry than D-3 and that the excitation energy can be transferred from one subchromophore to another within the lifetime of the excited state. Exciton-coupling theory was used to quantitatively analyze this excitation transfer.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据