cm8b01814_si_001.pdf (4.44 MB)
Singlet Fission in Core–Shell Micelles of End-Functionalized Polymers
journal contribution
posted on 2018-06-22, 16:48 authored by Andrew
J. Tilley, Ryan D. Pensack, Emily L. Kynaston, Gregory D. Scholes, Dwight S. SeferosSinglet
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.
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Spontaneous solution self-assemblytime-resolved fluorescence experiments evidencesolubilizing blocks influence singlet fission dynamicsequivalent singlet fission dynamicstriplet pair formationsinglet fission nanostructuressinglet fissionmolecule singlet fission chromophorescoretriplet pair lossesmicelleDLSPEGTEMEnd-Functionalized Polymers Singlet fissiontransmission electron microscopypolymer self-assemblyuse solution self-assembly
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