The
singlet fission (SF) process is generally defined as the conversion
of one singlet exciton (S1) into two triplet excitons (2·T1), which has the potential to overcome thermalization losses
in the field of photovoltaic devices. Among the applicable compounds
for SF-based photovoltaic devices, perylene bisimide (PBI) is one
of the best candidates because of its electronic tunability and photostability.
However, the strategy for efficient SF in PBIs remains ambiguous because
of numerous competing relaxation pathways in PBI-based molecular materials.
In this regard, for the first time, we observed the SF mechanism in
PBI dimers by controlling the intrinsic factor (exciton coupling)
and the external environment (solvent polarity and viscosity). Time-resolved
spectroscopic measurements and quantum chemical simulations reveal
that efficient SF occurs through the charge-transfer-assisted mechanism,
entailing a large structural fluctuation. Our findings not only highlight
the SF mechanism in PBI dimers but also suggest the factors responsible
for an efficient SF process, which are important considerations in
the design of molecular materials for photovoltaic devices.
Four well-defined π-stacks of perylene bisimide (PBI) dyes were obtained in solution by covalent linkage of two chromophores with spacer units of different length and sterical demand. Structural elucidation of the folda-dimers by in-depth nuclear magnetic resonance studies and geometry optimization at the level of density functional theory suggest different, but highly defined molecular arrangements of the two chromophores in the folded state enforced by the various spacer moieties. Remarkably, the dye stacks exhibit considerably different optical properties as investigated by UV/vis absorption and fluorescence spectroscopy, despite only slightly different chromophore arrangements. The distinct absorption properties can be rationalized by an interplay of long- and short-range exciton coupling resulting in optical signatures ranging from conventional H-type to monomer like absorption features with low and appreciably high fluorescence quantum yields, respectively. To the best of our knowledge, we present the first experimental proof of a PBI-based "null-aggregate", in which long- and short-range exciton coupling fully compensate each other, giving rise to monomer-like absorption features for a stack of two PBI chromophores. Hence, our insights pinpoint the importance of charge-transfer mediated short-range coupling that can significantly influence the optical properties of PBI π-stacks.
An adequately designed, bay-tethered perylene bisimide (PBI) dimer Bis-PBI was synthesized by Pd/Cu-catalyzed Glaser-type oxidative homocoupling of the respective PBI building block. This newly synthesized PBI dimer self-assembles exclusively and with high binding constants of up to 10 M into a discrete π-stack of four chromophores. Steady-state absorption and emission spectra show the signatures of H-type excitonic coupling among the dye units. Broadband fluorescence upconversion spectroscopy (FLUPS) reveals an ultrafast dynamics in the optically excited state. An initially coherent Frenkel exciton state that is delocalized over the whole quadruple stack rapidly (τ = ∼200 fs) loses its coherence and relaxes into an excimer state. Comparison with Frenkel exciton dynamics in PBI dimeric and oligomeric H-aggregates demonstrates that in the quadruple stack coherent exciton propagation is absent due to its short length of aggregates, thereby it has only one relaxation pathway to the excimer state. Furthermore, the absence of pump-power dependence in transient absorption experiments suggests that multiexciton cannot be generated in the quadruple stack, which is in line with time-resolved fluorescence measurements.
A triad based on triarylamine donors, an iridium dipyrrin sensitiser and a naphthalene diimide acceptor is investigated using fs-pump-probe spectroscopy at two different pump wavelengths. Excitation of the naphthalene diimide induces a stepwise electron transfer process that yields within ca. 100 ps a charge separated state with 50-60% quantum yield in which one triarylamine is oxidised and the imide is reduced. Although being in the Marcus normal region, this state has a lifetime of 580 ns in MeCN. Excitation at the dipyrrin ligand centred absorption directly produces the charge separated state within ca. 1 ns however without formation of an intermediate. This pseudo-concerted two-electron transfer step was analysed with the help of a model dyad and a modified triad and is interpreted to be caused by inverted electron transfer rates. Although being much slower the latter process has a quantum yield of practically 100%.
Single crystals of three at bay area tetraphenoxy‐substituted perylene bisimide dyes are grown by vacuum sublimation. X‐ray analysis reveals the self‐assembly of these highly twisted perylene bisimides (PBIs) in the solid state via imide–imide hydrogen bonding into hydrogen‐bonded PBI chains. The crystallographic insights disclose that the conformation and sterical congestion imparted by the phenoxy substituents can be controlled by ortho‐substituents. Accordingly, whilst sterically less demanding methyl and isopropyl substituents afford double‐stranded PBI chains of complementary P and M atropo‐enantiomers, single hydrogen‐bonded chains of homochiral PBIs are observed for the sterically more demanding ortho‐phenyl substituents. Investigation of the absorption and fluorescence properties of microcrystals and thin films of these PBIs allow for an unambiguous interpretation of these exciton systems. Thus, the J‐aggregates of the double‐stranded crystals exhibit a much larger (negative) exciton coupling than the single‐stranded one, which in contrast has the higher solid‐state fluorescence quantum yield.
For H-aggregates of perylene bisimide (PBI), it has been reported that upon photoexcitation, an initially delocalized Frenkel exciton is localized by excimer formation. However, in recent studies, the beforehand exciton dynamics preceding the excimer formation was suggested in larger aggregates consisting of at least more than 10-PBI subunits, which was not observed in small aggregates comprising less than four-PBI subunits. This feature implies that the size of molecular aggregates plays a crucial role in the initial exciton dynamics. In this regard, we have tried to unveil the initial exciton dynamics in PBI H-aggregates by tracking down the transient reorientations of electronic transition dipoles formed by interactions between the PBI subunits in systematically size-controlled PBI H-aggregates. The ultrafast coherent exciton dynamics depending on the molecular aggregate sizes can be distinguished using polarization-dependent femtosecond-transient absorption anisotropy spectroscopic measurements with a time resolution of ∼40 fs. The ultrafast decay profiles of the anisotropy values are unaffected by vibrational relaxation and rotational diffusion processes; hence, the coherent exciton dynamics of the PBI H-aggregates prior to the excimer formation can be directly revealed as the energy migration processes along the PBI H-aggregates.
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