Singlet Fission in Core–Shell Micelles of End-Functionalized Polymers

• Published in: Chemistry of materials Vol. 30; no. 13; pp. 4409 - 4421
• Main Authors: Tilley, Andrew J, Pensack, Ryan D, Kynaston, Emily L, Scholes, Gregory D, Seferos, Dwight S
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-07-2018; American Chemical Society (ACS)
• Subjects: Chemistry; Materials Science
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.8b01814

Singlet fission is the process in aggregates of molecular semiconductors where the initial product of light absorption (a singlet exciton) is converted into two correlated spin-triplet excitons. While most studies of singlet fission are conducted on assemblies of small molecule singlet fission chromophores, polymer self-assembly has yet to be explored as a means of creating nanostructures conducive for singlet fission. In this work, we use solution self-assembly of mono- and difunctionalized polymers to create core–shell micelles that display efficient singlet fission. The polymers are synthesized by copper­(I)-catalyzed “click” chemistry between a 6,13-bis­(triisopropyl­silylethynyl)­pentacene (TIPS-Pn) alkyne precursor and the corresponding azide-terminated poly­(ethylene glycol) (PEG) polymer. Spontaneous solution self-assembly creates starlike and flowerlike core–shell micelles that are characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM) experiments. Ultrafast transient absorption spectroscopy and time-resolved fluorescence experiments evidence nearly equivalent singlet fission dynamics in starlike and flowerlike micelles. Studies on mixed micelles of the Pn-functionalized polymer with a C16-PEG surfactant reveal how triplet pair formation and decay rates vary with micelle composition. The core–shell micelles developed herein demonstrate the potential of polymer self-assembly for creating functional singlet fission nanostructures and provide insight into how secondary components and solubilizing blocks influence singlet fission dynamics and triplet pair losses in self-assembled systems.