Singlet relaxation dynamics and long triplet lifetimes of thiophene-coupled perylene diimides dyads: New insights for high efficiency organic solar cells

In the active layer of organic solar cells (OSCs), the lifetime of triplet excitons is one of the decisive factors in the diffusion length and therefore has important impact on the power conversion efficiency of the devices. Herein, we have investigated singlet excited state relaxation dynamics and their triplet exciton lifetimes of two thiophene-coupled perylene diimides (PDI) dyads (2PDI-Th and fused-2PDI-Th), in order to provide a unique explanation in depth on their different performances in OSC devices. From the transient absorption (TA) spectra, the singlet excitons of 2PDI-Th form excimers in the time scale of 1.5 ps. Then the excimers go into the triplet state via intersystem crossing (ISC). In fused-2PDI-Th, triplet excitons are generated directly from the singlet excited excitons via the efficient ISC. Density functional theory (DFT) calculations further support the formation of excimers. DFT results indicate that 2PDI-Th exhibits an H-typed molecular configuration which is beneficial to form the excimers, while fused-2PDI-Th gives a twisted X-shaped configuration in the optimized ground and excited state. In steady-state emission spectra, 2PDI-Th shows abroad and featureless spectral characteristics of the excimers with a decay time of 840 ps, which is much shorter than those of PDI (5.5 ns) and fused-2PDI-Th (3.3 ns). The triplet lifetime (67 μs) of fused-2PDI-Th is factor of 3 longer than that of 2PDI-Th (22 μs). These results demonstrate that ring-fused structure is an efficient strategy to eliminate excimer formation and prolong the lifetime of triplet excitons, which provides a new insight for design of optoelectronic molecules for high efficiency organic solar cells.     

On the Influence of Higher Excited States on the ISC Quantum Yield of Octa-aL-alkyloxy-substituted Zn-Phthalocyanine Molecules Studied by Nonlinear Absorption

Abstract— Octa-aL-alkyloxy-substituted Zn-phthalocyanines are an interesting class of far red-absorbing photosensitizers. The chemical structure, the calculated steric conformation, the observed linear optical properties and an anomalous luminescence from a higher than S, excited state are reported. To study the optical properties of higher excited states and their occupation dynamics up to delay times of 15 ns we have carried out measurements of transient absorption spectra after 14 ps pulsed, resonant B-band and Q-band excitation. From these measurements the excited state singlet-singlet and triplet-triplet spectra as well as the intersystem crossing (ISC) quantum yields are obtained. The main result is an excitation wavelength-dependent ISC quantum yield that can be explained by an additional ISC channel between higher excited singlet and triplet states. The large rate of this channel is justified by the resonance between higher triplet states, observed in the triplet-triplet spectrum and the B, absorption band. Using kinetic model calculations, a lifetime of the higher excited singlet state of some picoseconds is predicted and the influence of a two-step absorption process on the population density of this higher excited singlet state is discussed.     

Study of acyl group migration by femtosecond transient absorption spectroscopy and computational chemistry

The primary photophysical and photochemical processes in the photochemistry of 1-acetoxy-2-methoxyanthraquinone (1a) were studied using femtosecond transient absorption spectroscopy. Excitation of 1a at 270 nm results in the population of a set of highly excited singlet states. Internal conversion to the lowest singlet npi* excited state, followed by an intramolecular vibrational energy redistribution (IVR) process, proceeds with a time constant of 150 +/- 90 fs. The 1npi* excited state undergoes very fast intersystem crossing (ISC, 11 +/- 1 ps) to form the lowest triplet pipi* excited state which contains excess vibrational energy. The vibrational cooling occurs somewhat faster (4 +/- 1 ps) than ISC. The primary photochemical process, migration of acetoxy group, proceeds on the triplet potential energy surface with a time constant of 220 +/- 30 ps. The transient absorption spectra of the lowest singlet and triplet excited states of 1a, as well as the triplet excited state of the product, 9-acetoxy-2-methoxy-1,10-anthraquinone (2a), were detected. The assignments of the transient absorption spectra were supported by time-dependent DFT calculations of the UV-vis spectra of the proposed intermediates. All of the stationary points for acyl group migration on the triplet and ground state singlet potential energy surfaces were localized, and the influence of the acyl group substitution on the rate constants of the photochemical and thermal processes was analyzed.     

Ligand-Localized Triplet-State Photophysics in a Platinum(II) Terpyridyl Perylenediimideacetylide

The synthesis, electrochemistry, and photophysical behavior of a Pt(II) terpyridyl perylenediimide (PDI) acetylide (1) charge-transfer complex is reported. The title compound exhibits strong (ε ≈ 5 × 10(4) M(-1)cm(-1)) low-energy PDI acetylide-based π-π* absorption bands in the visible range extending to 600 nm, producing highly quenched singlet fluorescence (Φ = 0.014 ± 0.001, τ = 109 ps) with respect to a nonmetalated PDI model chromophore. Nanosecond transient absorption spectroscopy revealed the presence of a long excited-state lifetime (372 ns in 2-methyltetrahydrofuran) with transient features consistent with the PDI-acetylide triplet state, ascertained by direct comparison to a model Pt(II) PDI-acetylide complex lacking low-energy charge-transfer transitions. For the first time, time-resolved step-scan FT-IR spectroscopy was used to characterize the triplet excited state of the PDI-acetylide sensitized in the title compound and its associated model complex. The observed red shifts (～30-50 cm(-1)) in the C═O and C≡C vibrations of the two Pt(II) complexes in the long-lived excited state are consistent with formation of the (3)PDI acetylide state and found to be in excellent agreement with the expected change in the relevant DFT-calculated IR frequencies in the nonmetalated PDI model chromophore (ground singlet state and lowest triplet excited state). Formation of the PDI triplet excited state in the title chromophore was also supported by sensitization of the singlet oxygen photoluminescence centered at ～1275 nm in air-saturated acetonitrile solution, Φ((1)O(2)) = 0.52. In terms of light emission, only residual PDI-based red fluorescence could be detected and no corresponding PDI-based phosphorescence was observed in the visible or NIR region at 298 or 77 K in the Pt(II) terpyridyl perylenediimideacetylide.     

Time-resolved EPR, fluorescence, and transient absorption studies on phthalocyaninatosilicon covalently linked to one or two TEMPO radicals.

The photophysical properties of tetra-tert-butylphthalocyaninatosilicon (SiPc) covalently linked to one or two 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radicals (R1, R2) have been studied by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance (TREPR) spectroscopies. It is found that the fluorescence quantum yields and lifetimes of R1 and R2 decrease compared with those of (dihydroxy)SiPc ((dihydroxy)SiPc = 6.8 ns, R1 = 4.7 ns and 42 ps, and R2 = 4.7 ns and <30 ps). Transient absorption measurements indicate that the lifetime of the excited triplet SiPc is markedly dependent on the number of linking TEMPO radicals ((dihydroxy)SiPc = 500 micros, R1 = 7.6 micros, and R2 = 3.7 micros). These short lifetimes of R1 and R2 in the excited states are explained as a result of the interaction with TEMPO changing the ISC between the singlet and triplet states to spin-allowed transitions. Quantitative TREPR investigations have been carried out for the radical-quartet pair mechanism of R1 and the photoinduced population transfer of R2. It is determined that the rise and decay times of these electron spin polarizations denote the spin-lattice relaxation time of the ground state and the lifetime of the excited multiplet state, respectively. This study contributes not only to an elucidation of radical-chromophore interactions but also to a novel approach for controlling magnetic properties by photoexcitation.     

Triplet formation involving a polar transition state in a well-defined intramolecular perylenediimide dimeric aggregate

A cofacially stacked perylenediimide (PDI) dimer with a xanthene linker was studied under a variety of conditions (solvent, temperature) and serves as a model for the molecular interactions occurring in solid films. Intrinsically, the PDI units have a fluorescence quantum yield (Phi F) close to unity, but Phi F is lowered by a factor of 6-50 at room temperature when two PDI moieties are held in a cofacial arrangement, while the decay time of the most emissive state is increased significantly (tau F = 27 ns in toluene) compared to a monomeric PDI molecule (tau F = 4 ns). Fluorescence measurements show a strong solvent and temperature dependence of the characteristics of the emissive excited state. In a glassy matrix of toluene (TOL) or 2-methyltetrahydrofuran (2-MeTHF), Phi F is high, and the decay time is long (tau F = approximately 50 ns). At higher temperature, both Phi F and tau F are reduced. Interestingly, at room temperature, Phi F and tau F are also reduced with increasing solvent polarity, revealing the presence of a polar transition state. Photoinduced absorption of the stacked molecules from the picosecond to the microsecond time scale shows that after photoexcitation reorganization occurs in the first nanoseconds, followed by intersystem crossing (ISC), producing the triplet excited state. Using singlet oxygen ( (1)Delta g) luminescence as a probe, a triplet quantum yield (Phi T) greater than 50% was obtained in air-saturated 2-Me-THF. Triplet formation is exceptional for PDI chromophores, and the enhanced ISC is explained by a decay involving a highly polar transition state.     

Time-resolved photoelectron spectroscopy of low-energy excitations of 4×4 C60/Cu(111)

Time-resolved two-photon photoemission is applied to investigate electron dynamics in multiple monolayers (MLs) of ordered fullerite on a copper substrate. The experimental data are analyzed assuming coupled excited state dynamics. Rate equations fitted to these dynamics yield lifetimes of about 80 ps for the lowest unoccupied molecular orbital (LUMO), about 1.2 ns for the singlet exciton and 22 μs for the triplet exciton at a surface temperature of 140 K. For trapped triplet excitons lifetimes up to 200 μs are observed. An increased excitation fluence reduces the lifetime of the excitons due to annihilation. An increased sample temperature slightly reduces the lifetime of the triplet exciton. There is no evident dependence of the exciton lifetimes on the pump photon energy in the range of hν = 2.9 to 3.3 eV. A dependence on the layer thickness (10-20 ML) is not observed as long as more than 9 ML are prepared.     

Ultrafast study of 9-diazofluorene: direct observation of the first two singlet states of fluorenylidene

Ultrafast photolysis of 9-diazofluorene (DAF) produces a broadly absorbing transient within the instrument time resolution (300 fs), which is assigned to an excited state of the diazo compound. The diazo excited state fragments to form fluorenylidene (Fl) in both its lowest energy singlet state (1Fl, 405-430 nm, depending on the solvent) and a higher energy singlet state (370 nm, 1Fl*). The excited singlet carbene has a lifetime of 20.9 ps in acetonitrile and decays to the lower energy singlet state (1Fl), which relaxes to the triplet ground state (3Fl) in acetonitrile, cyclohexane, benzene, and hexafluorobenzene. The equilibrium mixture of singlet and triplet fluorenylidene reacts with these solvents. Singlet fluorenylidene reacts with methanol and cyclohexene in competition with relaxation to 3Fl. One of the reaction products in methanol is the 9-fluorenyl cation. The rate of intersystem crossing (ISC) in hexafluorobenzene and other halogenated solvents is remarkably slow given that carbene ISC rates are generally fastest in nonpolar solvents. An explanation of this effect is advanced.     

Radical-Enhanced Intersystem Crossing in Perylene-Oxoverdazyl Radical Dyads

Attaching stable radicals to organic chromophores is an effective method to enhance the intersystem crossing (ISC) of the chromophores. Herein we prepared perylene-oxoverdazyl dyads either by directly connecting the two units or using an intervening phenyl spacer. We investigated the effect of the radical on the photophysical properties of perylene and observed strong fluorescence quenching due to radical enhanced ISC (REISC). Compared with a previously reported perylene-fused nitroxide radical compound (triplet lifetime, τ_T=0.1 μs), these new adducts show a longer-lived triplet excited state (τ_T=9.5 μs). Based on the singlet oxygen quantum yield (Φ_Δ=7 %) and study of the triplet state, we propose that the radical enhanced internal conversion also plays a role in the relaxation of the excited state. Femtosecond fluorescence up-conversion indicates a fast decay of the excited state (<1.0 ps), suggesting a strong spin-spin exchange interaction between the two units. Femtosecond transient absorption (fs-TA) spectra confirmed direct triplet state population (within 0.5 ps). Interestingly, by fs-TA spectra, we observed the interconversion of the two states (D₁↔Q₁) at ∼80 ps time scale. Time-resolved electron paramagnetic resonance (TREPR) spectral study confirmed the formation of the quartet sate. We observed triplet and quartet states simultaneously with weights of 0.7 and 0.3, respectively. This is attributed to two different conformations of the molecule at excited state. DFT computations showed that the interaction between the radical and the chromophore is ferromagnetic (J>0, 0.05∼0.10 eV).     

Solvent-Dependent Stabilization of a Charge Transfer State is the Key to Ultrafast Triplet State Formation in an Epigenetic DNA Nucleoside

2’-Deoxy-5-formylcytidine (5fdCyd), a naturally occurring nucleoside found in mammalian DNA and mitochondrial RNA, exhibits important epigenetic functionality in biological processes. Because it efficiently generates triplet excited states, it is an endogenous photosensitizer capable of damaging DNA, but the intersystem crossing (ISC) mechanism responsible for ultrafast triplet state generation is poorly understood. In this study, time-resolved mid-IR spectroscopy and quantum mechanical calculations reveal the distinct ultrafast ISC mechanisms of 5fdCyd in water versus acetonitrile. Our experiment indicates that in water, ISC to triplet states occurs within 1 ps after 285 nm excitation. PCM-TD-DFT computations suggest that this ultrafast ISC is mediated by a singlet state with significant cytosine-to-formyl charge-transfer (CT) character. In contrast, ISC in acetonitrile proceeds via a dark ¹nπ* state with a lifetime of ∼3 ps. CT-induced ISC is not favored in acetonitrile because reaching the minimum of the gateway CT state is hampered by intramolecular hydrogen bonding, which enforces planarity between the aldehyde group and the aromatic group. Our study provides a comprehensive picture of the non-radiative decay of 5fdCyd in solution and new insights into the factors governing ISC in biomolecules. We propose that the intramolecular CT state observed here is a key to the excited-state dynamics of epigenetic nucleosides with modified exocyclic functional groups, paving the way to study their effects in DNA strands.     

Accessing the Triplet State in Heavy‐Atom‐Free Perylene Diimides

Previous studies of perylenediimides (PDIs) mostly utilized the lowest singlet excited state S₁. Generation of a triplet excited state (T₁) in PDIs is important for applications ranging from photodynamic therapy to photovoltaics; however, it remains a formidable task. Herein, we developed a heavy‐atom‐free strategy to prompt the T₁←S₁ intersystem crossing (ISC) by introducing electron‐donating aryl (Ar) groups at the head positions of an electron‐deficient perylenediimide (PDI) core. We found that the ISC efficiency increases from 8 to 54 % and then to 86 % by increasing the electron‐donating ability of head‐substituted aryl groups from phenyl (p‐PDI) to methoxyphenyl (MeO‐PDI) and then to methylthioxyphenyl (MeS‐PDI). By enhancing the intramolecular charge‐transfer (ICT) interaction from p‐PDI to MeO‐PDI, and then to MeS‐PDI, singlet oxygen generation via energy‐transfer reactions from T₁ of PDIs to ³O₂ was demonstrated with the highest yield of up to 80 %. These results provide guidelines for developing new triplet‐generating PDIs and related rylene diimides for optoelectronic applications.     

Long-lived Triplet Excited State of Perylenemonoimide (PMI) in a Diimine Pt(II) Bis-acetylide Complex: Preparation and Study of the Photophysical Property with Transient Spectra

We prepared a N^N Pt(II) bisacetylide complex that has strong absorption of visible light (molar absorption coefficients ϵ=6.7×10⁴ M⁻¹ cm⁻¹ at 570 nm), and the singlet oxygen quantum yield (Φ_Δ) is up to 78 %. Femtosecond transient absorption spectra show the intersystem crossing (ISC) of the complex takes 81.8 ps, nanosecond transient absorption spectra show the triplet excited state lifetime is 7.6 μs. Density functional theory (DFT) computation demonstrated that the S₁ and T₁ states are mainly localized on the perylenemonoimide (PMI) ligands, although the involvement of the Pt(II) centre is noticeable. The complex was used as triplet photosensitizer to generate delayed fluorescence with perylenebisimide (PBI) as the triplet state energy acceptor and emitter, via the intermolecular triplet-triplet energy transfer (TTET) and triplet-triplet annihilation (TTA), the delayed fluorescence lifetime is up to 52.5 μs under the experimental conditions.     

Ultrafast study of p-biphenylyldiazomethane and p-biphenylylcarbene

p-Biphenylyldiazomethane was excited by femtosecond pulses of UV light in acetonitrile, in cyclohexane, and in methanol. Ultrafast photolysis produces a singlet excited state of p-biphenylyldiazomethane with lambdamax = 490 nm, and lifetimes of less than 300 fs in acetonitrile, in cyclohexane, and in methanol. The decay of the excited state is accompanied by the growth of transient absorption with lambdamax = 360 nm. The carrier of this transient absorption is attributed to singlet p-biphenylylcarbene, a result that is consistent with the predictions of TD-DFT calculations. The singlet carbene lifetimes are 200 and 77 ps in acetonitrile and cyclohexane, respectively, and are controlled by intersystem crossing to the lower energy triplet state. The transient absorption does not decay to baseline in acetonitrile, because of the formation of nitrile ylide. The equilibrium mixture of singlet and triplet p-biphenylylcarbene reacts with acetonitrile to form a nitrile ylide (lambdamax = 370 nm), and with cyclohexane by C-H insertion 1-20 ns after the laser pulse. The singlet carbene lifetime is only 7.9 ps in methanol, owing to a rapid reaction with the solvent. Reaction with the solvent gives rise, in part, to a p-biphenylylbenzyl cation (lambdamax = 450 nm, tau = 6.3 ps) in methanol.     

Triplet photophysics of gold(III) porphyrins

Gold porphyrins are often used as electron-accepting chromophores in donor-acceptor complexes for the study of photoinduced electron transfer, and they can also be involved in triplet-triplet energy-transfer interactions with other chromophores. Since the lowest excited singlet state is very short-lived (240 fs), the triplet state is usually the starting point for the transfer reactions, and it is therefore crucial to understand its photophysics. The triplet state of various gold porphyrins has been reported to have a lifetime of around 1.5 ns at room temperature and to have a biexponential decay both in emission and in transient absorption with decay times of around 10 and 100 micros at 80 K. In this paper, the triplet photophysics of two gold porphyrins (Au(III) 5,15-bis(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin and Au(III) 5,10,15,20-tetra(3,5-di-tert-butylphenyl)porphyrin) are studied by steady-state and time-resolved absorption and emission spectroscopy over a wide temperature range (4-300 K). The study reveals the existence of a dark state with an approximate lifetime of 50 ns, which was not previously observed. This state acts as an intermediate between the short-lived singlet and the triplet state manifold. In addition, we present DFT calculations, in which the core electrons of the central metal were replaced by a pseudopotential to account for the relativistic effects, which suggest that the lowest excited singlet state is an optically forbidden ligand-to-metal charge-transfer (LMCT) state. This LMCT state is an obvious candidate for the experimentally observed dark state, and it is shown to dictate the photophysical properties of gold porphyrins by acting as a gate for triplet state formation versus direct return to the ground state.     

On the molecular conformation of bisaromatic systems the case of 2-phenyl-2H-benzotriazoles

2-Phenyl-2H-benzotriazole exhibits a planar molecular conformation both in its ground electronic state (S₀) and its first excited singlet (S₁) and triplet state (T₁). However, introducing one or two methyl groups in the ortho positions of the phenyl ring causes the aromatic systems in the compound to lose their coplanarity in both S₀ and T₁ electronic states. On the other hand, 2-(2-methylphenyl)-2H-benzotriazole regains such coplanarity in its first excited singlet state S₁, giving rise to population inversion that could be used to generate stimulated radiation around 350 nm.

As shown in this work, the effectiveness of the ISC process in these compounds is markedly dependent on the twisting angle, θ, of the structure; accordingly, ISC occurs to a negligible extent in a planar compound such as 2-phenyl-2H-benzotriazole, where θ = 0°. This evidence supports the assumption that planar molecular forms of the TIN-P photoprotectors are more photostable than non-planar ones due to the non effective generation via ISC of their triplet states.     

Electronic spectra and luminescence properties of 1,2-benzotetraphene in crystalline matrices at 77 K

Quasilinear absorption and luminescence spectra of 1,2-benzotetraphene were obtained in polycrystalline matrices at 77 K. Tne energies of successive excited singlet states as well as the energy of the lowest excited triplet state were found experimentally and compared with those calculated by the PPP CI method. The fluorescence lifetime and quantum yield were determined experimentally. Moreover, the radiationless transition probabilities, lifetime of triplet state and phosphorescence quantum yield were estimated employing the Siebrand-Williams model. The results obtained suggest that radiationless ISC processes are the main deactivation channel of the S₁ and T₁ states. The vibrational analysis of quasilinear absorption and luminescence spectra was performed and fundamental frequencies of ground and first excited singlet states were determined.     

Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions

We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.     

Intramolecular photoexcitation dynamics and magnetic field effects in an intermediate-case molecule

Molecular vibration and rotation play a significant role in the intramolecular photoexcitation dynamics of the so-called intermediate-case molecule, and the fluorescence intensity, decay and polarization of s-triazine vapor are shown to depend on the excited rovibronic level of the S₁ state. Fluorescence characteristics are interpreted by assuming three zero-order states: (1) a zero-order singlet state that carries the absorption intensity and emits fluorescence with sharp structure; (2) zero-order singlet states that do not carry the absorption intensity but emit broad fluorescence; and (3) zero-order triplet states. The interaction among these states depends not only on the vibrational level but also on the rotational level excited. It is suggested that the number of triplet states coupled to the singlet state increases with increasing excess vibrational energy. It is also suggested that K-scrambling occurs both in the triplet manifold following intersystem crossing (ISC) and in the singlet manifold following intramolecular vibrational energy redistribution (IVR). The fluorescence intensity and decay of s-triazine vapor are significantly influenced by a magnetic field, and the field effects are interpreted in terms of the spin decoupling in the triplet manifold following ISC; the role of external magnetic fields is to mix the spin sublevels of different rovibronic levels coupled to the excited singlet state. Magnetic depolarization of fluorescence also occurs because of the efficient interaction between the excited singlet state and the triplet state.     

The gold porphyrin first excited singlet state

Gold porphyrins are often used as electron-accepting chromophores in artificial photosynthetic constructs. Because of the heavy atom effect, the gold porphyrin first-excited singlet state undergoes rapid intersystem crossing to form the triplet state. The lowest triplet state can undergo a reduction by electron donation from a nearby porphyrin or another moiety. In addition, it can be involved in triplet-triplet energy transfer interactions with other chromophores. In contrast, little has been known about the short-lived singlet excited state. In this work, ultrafast time-resolved absorption spectroscopy has been used to investigate the singlet excited state of Au(III) 5,15-bis(3,5-di-t-butylphenyl)-2,8,12,18,-tetraethyl-3,7,13,17-tetramethylporphyrin in ethanol solution. The excited singlet state is found to form with the laser pulse and decay with a time constant of 240 fs to give the triplet state. The triplet returns to the ground state with a life-time of 400 ps. The lifetime of the singlet state is comparable with the time constants for energy and photoinduced electron transfer in some model and natural photosynthetic systems. Thus, it is kinetically competent to take part in such processes in suitably designed supermolecular systems.     

Excited-state symmetry breaking in cofacial and linear dimers of a green perylenediimide chlorophyll analogue leading to ultrafast charge separation

Photoexcitation of chromophoric dimers constrained to a symmetric pi-stacked geometry by their molecular structure usually produces excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular pi systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 1,7-bis(pyrrolidin-1'-yl)-perylene-3,4:9,10-bis(dicarboximide) (5PDI) in the low polarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PDI2, was synthesized by attaching two 5PDI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PDI2, was prepared in which the 5PDI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge pi systems of the 5PDI chromophores within lin-5PDI2 are perpendicular to one another. Ground-state absorption spectra of both 5PDI dimers show exciton coupling, which is consistent with the orientation of the 5PDI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 700 nm, 100 fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PDI2 in toluene with tau = 0.17 ps followed by charge recombination to the ground state with tau = 222 ps. Similar measurements on lin-5PDI2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein tau = 55 ps for charge separation and tau = 99 ps for charge recombination. Excited-state symmetry breaking in 5PDI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.