The Role of the Core Attachment Positioning in Triggering Intramolecular Singlet Exciton Fission in Perylene Diimide Tetramers.

Previous studies have proposed that the presence of a flexible π-bridge linker is crucial in activating intramolecular singlet exciton fission (iSEF) in multichromophoric systems. In this study, we report the photophysical properties of three analogous perylene diimide (PDI) dendritic tetramers showing flexible/twisted π-bridged structures with α- and ß-substitutions and a rigid/planar structure with a ß-fused ring (ßC) connection to a benzodithiophene-thiophene (BDT-Th) core. The rigidity and enhanced planarity of ßC lead to significant intramolecular charge transfer and triplet formation via an intersystem crossing pathway. Steady-state spectroscopic measurements reveal similar absorption and emission spectra for the α-tetramer and the parent PDI monomer. However, their fluorescence quantum yield is significantly different. The negligible fluorescence yield of the α-tetramer (0.04%) is associated with a competitive nonradiative decay pathway. Indeed, for this twisted compound in a high polar environment, a fast and efficient iSEF with a triplet quantum yield of 124% is observed. Our results show that the α-single-bond connections in the α compound are capable of interrupting the coupling among the PDI units, favoring iSEF. We propose that the formation of the double triplet (1[TT]) state is through a superposition of singlet states known as [S1S0][TT]CT, which has been suggested previously for pentacene derivatives. Using steady-state and time-resolved spectroscopic experiments, we demonstrate that the conformational flexibility of the linker itself is necessary but not sufficient to allow iSEF. For the case of the other twisted tetramer, ß, the strong π-π co-facial interactions between the adjacent PDI units in its structure lead to excimer formation. These excimer states trap the singlet excitons preventing the formation of the 1[TT] state, thus inhibiting iSEF.

New Direct Approach for Determining the Reverse Intersystem Crossing Rate in Organic Thermally Activated Delayed Fluorescent (TADF) Emitters.

We developed a new optical method to determine the rate of reverse intersystem crossing (krISC) in thermally activated delayed fluorescent (TADF) organic chromophores using time-resolved transient absorption spectroscopy. We successfully correlated the krISC of the TADF-chromophores with device performance. Specifically, we focused on the external quantum efficiency (ηEQE) and the stability of the device at high brightness levels. It is believed that by obtaining a large krISC one may reduce the possibility of triplet-triplet annihilation (TTA) and increase the long-term stability of organic light emitting diodes (OLEDs) devices at high brightness levels (ηEQE roll-off). In this contribution, we investigate the photophysical mechanism in a series of TADF-chromophores based on carbazole or acridine derivatives as donor moieties, and triazine or benzonitrile derivatives as the acceptor moieties. We found a relationship between large krISC values and high ηEQE values at low operating voltages for the TADF-chromophores investigated. In addition, those chromophores with a larger krISC illustrated a smaller ηEQE roll-off (higher stability) at high operating voltages. These features are beneficial for superior OLEDs performing devices. Contrarily, we found that if a chromophore has a krISC ≤ 105s-1 its ηEQE is ≤5%. Such a small krISC suggests that there is no TADF effect operating in these organic systems and the molecule is not efficient in harvesting triplet excitons. Emission lifetime-based methodologies for determining the krISC were included for comparison but failed to predict the devices performance of the investigated TADF-chromophores to the same extent of our proposed methodology.

Activating intramolecular singlet exciton fission by altering π-bridge flexibility in perylene diimide trimers for organic solar cells.

In this study, two analogous perylene diimide (PDI) trimers, whose structures show rotatable single bond π-bridge connection (twisted) vs. rigid/fused π-bridge connection (planar), were synthesized and investigated. We show via time resolved spectroscopic measurements how the π-bridge connections in A-π-D-π-A-π-D-π-A multichromophoric PDI systems strongly affect the triplet yield and triplet formation rate. In the planar compound, with stronger intramolecular charge transfer (ICT) character, triplet formation occurs via conventional intersystem crossing. However, clear evidence of efficient and fast intramolecular singlet exciton fission (iSEF) is observed in the twisted trimer compound with weaker ICT character. Multiexciton triplet generation and separation occur in the twisted (flexible-bridged) PDI trimer, where weak coupling among the units is observed as a result of the degenerate double triplet and quintet states, obtained by quantum chemical calculations. The high triplet yield and fast iSEF observed in the twisted compound are due not only to enthalpic viability but also to the significant entropic gain allowed by its trimeric structure. Our results represent a significant step forward in structure-property understanding, and may direct the design of new efficient iSEF materials.