Fluorescence Quenching in J-Aggregates through the Formation of Unusual Metastable Dimers
Witte, Felix and Rietsch, Philipp and Sinha, Shreya and Krappe, Alexander and Joswig, Jan-O. and Götze, Jan P. and Nirmalananthan-Budau, Nithiya and Resch-Genger, Ute and Eigler, Siegfried and Paulus, Beate – 2021
Molecular aggregation alters the optical properties of a system as fluorescence may be activated or quenched. This is usually described within the well-established framework of H- and J-aggregates. While H-aggregates show nonfluorescent blueshifted absorption bands with respect to the isolated monomer, J-aggregates are fluorescent displaying a redshifted peak. In this publication, we employ a combined approach of experiment and theory to study the complex aggregation features and photophysical properties of diaminodicyanoquinone derivatives, which show unusual and puzzling nonfluorescent redshifted absorption bands upon aggregation. Our theoretical analysis demonstrates that stable aggregates do not account for the experimental observations. Instead, we propose an unprecedented mechanism involving metastable dimeric species formed from stable dimers to generate nonfluorescent J-aggregates. These results represent a novel kind of aggregation-induced optical effect and may have broad implications for the photophysics of dye aggregates.