Silylethynyl substitution for preventing aggregate formation in perylene diimides

Abstract

Ethynylene-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.