Structure and photophysics of indigoids for singlet fission: Cibalackrot.

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model.

Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran.

Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such "excitation isomerism" is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

Mechanism of singlet fission in thin films of 1,3-diphenylisobenzofuran.

In order to elucidate the mechanism of singlet fission in thin films of 1,3-diphenylisobenzofuran (1) we have performed ultrafast transient absorption spectroscopy as a function of sample temperature and excitation fluence on polycrystalline thin films composed of two polymorphs. Our earlier investigations revealed that films enriched in a particular polymorph of 1 displayed near 200% efficiency for triplet formation at 77 K, while films composed primarily of a second polymorph had a very low triplet quantum yield. Present data confirm the triplet yield disparities in the two polymorphs and demonstrate the distinct fates of the initially prepared singlets in films of different structure. Singlet fission is inhibited in the more stable polymorph due to rapid excimer formation and trapping. The less stable polymorph undergoes highly efficient singlet fission with a dominant time constant of 10-30 ps and without strong thermal activation. Transient absorption measurements with varying excitation fluence indicate that singlet-singlet annihilation is a primary competitor of singlet fission at higher fluence and that fission from higher-lying states can also contribute to the triplet formation process. Measurements employing different excitation energies and sample temperatures reveal the role that trapping processes play in attenuating the triplet quantum yield to produce the complex temperature dependence of the singlet fission yield. The rate constants for singlet fission itself are essentially temperature independent.

Polymorphism influences singlet fission rates in tetracene thin films.

We report the effect of crystal structure and crystallite grain size on singlet fission (SF) in polycrystalline tetracene, one of the most widely studied SF and organic semiconductor materials. SF has been comprehensively studied in one polymoprh (Tc I), but not in the other, less stable polymorph (Tc II). Using carefully controlled thermal evaporation deposition conditions and high sensitivity ultrafast transient absorption spectroscopy, we found that for large crystallite size samples, SF in nearly pure Tc II films is significantly faster than SF in Tc I films. We also discovered that crystallite size has a minimal impact on the SF rate in Tc II films, but a significant influence in Tc I films. Large crystallites exhibit SF times of 125 ps and 22 ps in Tc I and Tc II, respectively, whereas small crystallites have SF times of 31 ps and 33 ps. Our results demonstrate first, that attention must be paid to polymorphism in obtaining a self-consistent rate picture for SF in tetracene and second, that control of polymorphism can play a significant role towards achieving a mechanistic understanding of SF in polycrystalline systems. In this latter context we show that conventional theory based on non-covalent tetracene couplings is insufficient, thus highlighting the need for models that capture the delocalized and highly mobile nature of excited states in elucidating the full photophysical picture.

Photocurrent enhanced by singlet fission in a dye-sensitized solar cell.

Investigations of singlet fission have accelerated recently because of its potential utility in solar photoconversion, although only a few reports definitively identify the role of singlet fission in a complete solar cell. Evidence of the influence of singlet fission in a dye-sensitized solar cell using 1,3-diphenylisobenzofuran (DPIBF, 1) as the sensitizer is reported here. Self-assembly of the blue-absorbing 1 with co-adsorbed oxidation products on mesoporous TiO2 yields a cell with a peak internal quantum efficiency of ∼70% and a power conversion efficiency of ∼1.1%. Introducing a ZrO2 spacer layer of thickness varying from 2 to 20 Šmodulates the short-circuit photocurrent such that it is initially reduced as thickness increases but 1 with 10-15 Šof added ZrO2. This rise can be explained as being due to a reduced rate of injection of electrons from the S1 state of 1 such that singlet fission, known to occur with a 30 ps time constant in polycrystalline films, has the opportunity to proceed efficiently and produce two T1 states per absorbed photon that can subsequently inject electrons into TiO2. Transient spectroscopy and kinetic simulations confirm this novel mode of dye-sensitized solar cell operation and its potential utility for enhanced solar photoconversion.