RESUMEN
The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500-800 cm(-1) region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. The vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules.
RESUMEN
The encapsulation efficiency of high-Tg polynorbornene micelles was probed with a hydrophobic dye 2,6-diiodoboron-dipyrromethene (BODIPY). Changes in the visible absorption spectra of aggregated versus monomeric dye molecules provided a probe for assessing encapsulation. Polynorbornene micelles are found to be capable of loading up to one BODIPY dye per ten polymers. As the hydrophilic block size increased in the polymeric amphiphiles, more of the dye was incorporated within the micelles. This result is consistent with the dye associating with the polymer backbone in the shell of the micelles. The encapsulation rate varied significantly with temperature, and a slight dependence on micellar morphology was also noted. Additionally, we report a 740 µs triplet lifetime for the encapsulated BODIPY dye. The lifetime is the longest ever recorded for a BODIPY triplet excited state at room temperature and is attributed to hindered triplet-triplet annihilation in the high-viscosity micellar shell.