Energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is often limited by formation of a low-energy excimer state. Formation dynamics of excimer states are often characterized by line shape changes and peak shift dynamics in femtosecond visible transient absorption spectra. Femtosecond near-infrared transient absorption experiments reveal a unique low-energy transition that can be used to identify and characterize this state without overlapping excited singlet-state absorption. Three covalently bound PDI dimers with differing PDI-PDI distances were studied to probe the influence of interchromophore electronic coupling on the PDI excimer transient spectra and dynamics.

We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI(+•)-PDI(-•) in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI(+•)-PDI(-•) to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Robust perylene-3,4-dicarboximide (PMI) π-aggregates provide important light-harvesting and electron-hole pair generation advantages in organic photovoltaics and related applications, but relatively few studies have focused on the electronic interactions between PMI chromophores. In contrast, structure-function relationships based on π-π stacking in the related perylene-3,4:9,10-bis(dicarboximides) (PDIs) have been widely investigated. The performance of both PMI and PDI derivatives in organic devices may be limited by the formation of low-energy excimer trap states in morphologies where interchromophore coupling is strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ~1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state absorption appears in ~1 ps, followed by conformational relaxation over 8-17 ps. The excimer state then decays in 6.9-12.8 ns, as measured by time-resolved fluorescence spectroscopy. The excimer lifetimes reach a maximum for a slip-stacked geometry in which the two PMI molecules are displaced along their long axes by one phenyl group (~4.3 Å). Additional displacement of the PMIs by a biphenyl spacer along the long axis prevents excimer formation. Symmetry-breaking charge transfer is not observed in any of the PMI dimers, and only a small triplet yield (<5%) is observed for the cofacial PMI dimers. These data provide structural insights for minimizing excimer trap states in organic devices based on PMI derivatives.

The ultrafast vibrational dynamics of the photoinduced charge-transfer reaction between perylene (Per) and perylene-3,4:9,10-bis(dicarboximide) (PDI) were investigated using femtosecond stimulated Raman spectroscopy (FSRS). Specifically probing the structural dynamics of PDI following its selective photoexcitation in a covalently linked dyad reveals vibrational modes uniquely characteristic to the PDI lowest excited singlet state and radical anion between 1000 and 1700 cm(-1). A comparison of these vibrations to those of the ground state reveals the appearance of new (1*)PDI and PDI(-•) stretching modes in the dyad at 1593 and 1588 cm(-1), respectively. DFT calculations reveal that these vibrations are parallel to the long axis of PDI and thus then may be integral to the charge separation reaction. The ability to differentiate excited state from radical anion vibrational modes allows the evaluation of the influence of specific modes on the charge transfer dynamics in donor-bridge-acceptor systems based on PDI molecular constructs.

Two covalent perylene-3,4:9,10-bis(dicarboximide) (PDI) dimers in which the PDI molecules are attached to a xanthene (Xan) scaffold in which the long axes of the two π-π stacked PDI molecules are slipped by 4.3 and 7.9 Å were prepared. These dimers are designed to mimic J-aggregates and provide insights into the photophysics of triplet state formation in PDI aggregates that target organic electronics. Using ultrafast transient absorption and stimulated Raman spectroscopy, the mechanism of (3)*PDI formation was found to depend strongly on a competition between the rate of Xan(•+)-PDI(•-) formation involving the spacer group and the rate of excimer-like state formation. Which mechanism is favored depends on the degree of electronic coupling between the two PDI molecules and/or solvent polarity. Singlet exciton fission to produce (3)*PDI does not compete kinetically with these processes. The excimer-like state decays relatively slowly with τ = 28 ns to produce (3)*PDI, while charge recombination of Xan(•+)-PDI(•-) yields (3)*PDI more than an order of magnitude faster. The perpendicular orientation between the π orbitals of PDI and the Xan bridge provides a large enough orbital angular momentum change to greatly increase the intersystem crossing rate via Xan(•+)-PDI(•-) → (3)*PDI charge recombination. These results highlight the importance of understanding inter-chromophore electronic coupling in a wide range of geometries as well as the active role that molecular spacers can play in the photophysics of covalent models for self-assembled chromophore aggregates.