Effect of Substituents at Imide Positions on the Laser Performance of 1,7-Bay-Substituted Perylenediimide Dyes

Perylenediimide (PDI) compounds with no substituents in their core are widely used as the active units of thin-film organic lasers. Recently, bay-substituted PDIs (b-PDIs) bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received great attention because they show red-shifted emission with respect to bay-unsubstituted PDIs, while maintaining high photoluminescence (PL) quantum yields and low amplified spontaneous emission (ASE) thresholds even at high doping rates. However, their ASE photostability is relatively low compared to that of state-of-the-art PDIs. Thus, the design of b-PDIs with improved ASE photostability remains a challenge. Here, the synthesis of two b-PDIs with phenyl-type substituents at the imide positions is reported. Complete characterization of their optical properties, including absorption, PL, ASE, and transient spectroscopy, supported also by quantum chemical calculations, is performed with the dyes diluted in either a liquid solvent or a polystyrene film. Film experiments were accomplished at very low doping rates, to resemble the isolated molecule behavior, and also in a range of increasing doping rates, to investigate concentration quenching effects. The reported b-PDIs show improved ASE photostability (3-fold) with respect to b-PDIs with aliphatic-type substituents at the imide positions, whilst they show more propensity toward aggregation.The authors thank the Spanish Ministry of Economy and Competitiveness MINECO and the European Social Funds (project MAT2015-66586-R and FPI fellowship BES-2016-077681), the Ministry of Science and Innovation (MICINN) and the European FEDER funds (CTQ2016-77039-R, PGC2018-099568-B-I00, and PID2019-109200GB-I00, and Unidad de Excelencia María de Maeztu CEX2019-000919-M), and the Generalitat Valenciana (PROMETEO/2020/077 and SEJI/2018/035). J.A. acknowledges the MICINN for the “Ramón-y-Cajal” Fellowship (RyC-2017-23500)