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Öğe The Effect of Imide Substituents on the Excited State Properties of Perylene Diimide Derivatives(2022) Danos, Andrew; Li, Chunyong; Monkman, Andrew; Varlıklı, Canan; Aksoy, ErkanSolid state optical properties of fluorescent materials are important for many photonic devices such as organic light emitting diodes, frequency down-converters or luminescent solar concentrators. Perylene diimides (PDIs) represent one of the most popular organic semiconductors which find application in such photonic device applications. In this study, photophysical properties of two dibrominated PDI (DiBrPDIs), one of which contains a branched alkyl chain (2-ethylhexyl, 2-EH) and the other with an aromatic substituent (diisopropylphenyl, DIA) at the imide positions are comparatively studied. We report their absorption and photoluminescence, lifetime and photoluminescence quantum yield (PLQY), as well as photoinduced absorption properties (PIA) examined by fs-transient absorption spectroscopy. Having the same ? conjugated system, DiBrPDIDIA and DiBrPDI-2EH exhibited identical absorption and photoluminescence (PL) spectra in chloroform (?abs:527 nm and ?PL:552 nm). However, in film phase, DiBrPDI-DIA (?PL-DIA:596 nm; PLQY:73.4%) presented a shorter PL wavelength with a higher PLQY than that of DiBrPDI-2EH (?PL-2EH:649 nm; PLQY:36.7%). Bond lengths and core bending angles of PDI derivatives were calculated using Chem3D pro software. It was determined that the 2,6-diisopropylphenyl group in DiBrPDI(DIA) extends a distance of about 6.8 Å out from the imide positions, providing more effective steric protection from aggregation than the smaller 2EH group.Öğe Silylethynyl Substitution for Preventing Aggregate Formation in Perylene Diimides(Amer Chemical Soc, 2021) Aksoy, Erkan; Danos, Andrew; Li, Chunyong; Monkman, Andrew P.; Varlikli, CananEthynylene-bridged perylene diimides (PDIs) with different sized silane groups have been synthesized as a steric blocking group to prevent the formation of non-radiative trap sites, for example, strong H-aggregates and other dimers or excimers. Excited singlet-state exciton dynamics were investigated by time-resolved photoluminescence and ultrafast pump-probe transient absorption spectroscopy. The spectra of the excimer or dimer aggregates formed by the PDIs at high concentrations were also determined. Although the photophysical properties of the bare and shielded PDIs are identical at micromolar concentrations, more shielded PDI2 and PDI3 exhibited resistance to aggregation, retaining higher photoluminescence quantum yield even at 10 mM concentration and in neat films. The PDIs also exhibited high photostability (1 h of continuous excitation), as well as electrochemical stability (multiple cycles with cyclic voltammetry). Prevention of dimer/aggregate formation in this manner will extend the uses of PDIs to a variety of high concentration photonics and optoelectronic applications, such as organic light-emitting diodes, organic photovoltaics, and luminescent solar concentrators.