Singlet fission (SF) in polycrystalline thin films of four 3,6-bis(thiophen-2-yl)diketopyrrolopyrrole (TDPP) chromophores with methyl (Me), n-hexyl (C6), triethylene glycol (TEG), and 2-ethylhexyl (EH) substituents at the 2,5-positions is found to involve an intermediate excimer-like state. The four different substituents yield four distinct intermolecular packing geometries, resulting in variable intermolecular charge transfer (CT) interactions in the solid. SF from the excimer state of Me, C6, TEG, and EH takes place in τSF = 22, 336, 195, and 1200 ps, respectively, to give triplet yields of 200%, 110%, 110%, and 70%, respectively. The transient spectra of the excimer-like state and its energetic proximity to the lowest excited singlet state in these derivatives suggests that this state may be the multiexciton (1)(T1T1) state that precedes formation of the uncorrelated triplet excitons. The excimer decay rates correlate well with the SF efficiencies and the degree of intermolecular donor-acceptor interactions resulting from π-stacking of the thiophene donor of one molecule with the DPP core acceptor in another molecule as observed in the crystal structures. Such interactions are found to also increase with the SF coupling energies, as calculated for each derivative. These structural and spectroscopic studies afford a better understanding of the electronic interactions that enhance SF in chromophores having strong intra- and intermolecular CT character.

Singlet exciton fission (SF) is a promising strategy for increasing photovoltaic efficiency, but in order for SF to be useful in solar cells, it should take place in a chromophore that is air-stable, highly absorptive, solution processable, and inexpensive. Unlike many SF chromophores, diketopyrrolopyrrole (DPP) conforms to these criteria, and here we investigate SF in DPP for the first time. SF yields in thin films of DPP derivatives, which are widely used in organic electronics and photovoltaics, are shown to depend critically on crystal morphology. Time-resolved spectroscopy of three DPP derivatives with phenyl (3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhDPP), thienyl (3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, TDPP), and phenylthienyl (3,6-di(5-phenylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhTDPP) aromatic substituents in 100-200 nm thin films reveals that efficient SF occurs only in TDPP and PhTDPP (τSF = 220 ± 20 ps), despite the fact that SF is most exoergic in PhDPP. This result correlates well with the greater degree of π-overlap and closer π-stacking in TDPP (3.50 Å) and PhTDPP (3.59 Å) relative to PhDPP (3.90 Å) and demonstrates that SF in DPP is highly sensitive to the electronic coupling between adjacent chromophores. The triplet yield in PhTDPP films is determined to be 210 ± 35% by the singlet depletion method and 165 ± 30% by the energy transfer method, showing that SF is nearly quantitative in these films and that DPP derivatives are a promising class of SF chromophores for enhancing photovoltaic performance.

Singlet fission (SF) is a spin-allowed process that involves absorption of a photon by two electronically interacting chromophores to produce a singlet exciton state, (SS), followed by rapid formation of two triplet excitons if the singlet exciton energy is about twice that of the triplet exciton. The initial formation of the multiexciton correlated triplet pair state, (TT), is thought to involve the agency of charge transfer (CT) states. The dynamics of these electronic states were studied in a covalent slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer in which the conformation of two TDI molecules is determined by a xanthene spacer (XanTDI). Femtosecond mid-infrared (fsIR) spectroscopy shows that the multiexciton (TT) state has absorptions characteristic of the T state in the carbonyl stretch region of the IR spectrum, in addition to IR absorptions specific to the CT state in the C═C stretch region. The simultaneous presence of CT and triplet state features in both high dielectric constant CHCl and low dielectric constant 1,4-dioxane throughout the multiexciton state lifetime suggests that this state has both CT and triplet character.

Layered perovskites are hybrid two-dimensional materials, formed through the self-assembly of inorganic lead halide networks separated by organic ammonium cation layers. In these natural quantum-well structures, quantum and dielectric confinement lead to strongly bound excitonic states that depend sensitively on the material composition. In this article, we review current understanding of exciton photophysics in layered perovskites and highlight the many ways in which their excitonic properties can be tuned. In particular, we focus on the coupling of exciton dynamics to lattice motion and local distortions of the soft and deformable hybrid lattice. These effects lead to complex excited-state dynamics, presenting new opportunities for design of optoelectronic materials and exploration of fundamental photophysics in quantum confined systems.

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