Delocalized Excitation or Intramolecular Energy Transfer in Pyrene Core Dendrimers.

Light-harvesting and then intramolecular energy transfer are the crucial steps in natural photosynthesis. Dendrimers are one of the most promising artificial light-harvesting antennas. Insight into the relationship between molecular structure and energy transfer (or delocalized excitation) in dendrimers would help in understanding and mimicking photosynthesis. Here, a series of dendrimers T1-T4 based on pyrene as a core and fluorene/carbazole as the dendrons have been studied with time-resolved fluorescence and femtosecond transient absorption spectroscopies, revealing that the large planar structure of T1 and T2 has led to strong coupling of pyrene and fluorene units, enabling delocalized excitation over the entire molecules. But for T3 and T4, the carbazole units linking the first- and second-generation branches have broken the planar structure and suppressed the π-electron delocalization, enabling the Forster resonance energy transfer. The efficient intramolecular energy transfer from peripheral branches to the core occurs within 2 ps.