Institut für Organische Chemie, Universität Würzburg, Wilhelm Conrad Röntgen Research Center for Complex Material Systems, Würzburg, Germany.
J Org Chem. 2012 Jul 20;77(14):6147-54. doi: 10.1021/jo300924x. Epub 2012 Jul 6.
Two different hexaarylbenzenes with three pyrene and three triarylamine substituents in different positions (trigonal symmetric and asymmetric arrangement) were synthesized, and their charge-transfer states were investigated by optical spectroscopy. In these multichromophoric systems triarylamine acts as the electron donor and pyrene as the electron acceptor. A reference chromophore with only one donor-acceptor pair was also investigated. All these chromophores form charge-transfer states upon photoexcitation which relax with a moderate fluorescence quantum yield to the ground state. The compounds do not differ significantly concerning most of their fluorescence properties, which shows that the fluorescent charge-transfer state is very similar in all chromophores. This observation indicates symmetry breaking for the symmetric chromophore within fluorescence lifetime of several tens of ns. This interpretation was substantiated by fluorescence excitation anisotropy measurements in a sucrose octaacetate matrix.
两种具有不同取代位置(三角对称和不对称排列)的三芘和三苯胺取代的六芳基苯被合成出来,并通过光谱学研究了它们的电荷转移态。在这些多生色团体系中,三苯胺作为电子供体,芘作为电子受体。还研究了一个只有一个给体-受体对的参比生色团。所有这些生色团在光激发下形成电荷转移态,然后以中等的荧光量子产率弛豫到基态。这些化合物在大多数荧光性质方面没有显著差异,这表明在所有生色团中,荧光电荷转移态非常相似。这种观察表明,在几十纳秒的荧光寿命内,对称生色团的对称性被打破。这种解释通过在蔗糖八乙酸酯基质中的荧光激发各向异性测量得到了证实。