Symmetry-breaking Charge Separation Research Articles

Photo‐Induced Ultrafast Charge Transfer and Air‐Stable Radical Formation in Tetraphenylpyrene Derivatives

AbstractStable organic radicals generated by photo‐excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo‐generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8‐tetraphenylpyrene derivative (Py‐TTAc) displaying photo‐induced radicals with air stability in the solid state. Photo‐induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py‐TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X‐ray technology suggests that the radicals are derived from photo‐induced symmetry‐breaking charge separation (SB‐CS) and stabilized through non‐covalent interactions. The photo‐generated stable radical system is employed in anti‐counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Photo-Induced Ultrafast Charge Transfer and Air-Stable Radical Formation in Tetraphenylpyrene Derivatives.

Stable organic radicals generated by photo-excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo-generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8-tetraphenylpyrene derivative (Py-TTAc) displaying photo-induced radicals with air stability in the solid state. Photo-induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py-TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X-ray technology suggests that the radicals are derived from photo-induced symmetry-breaking charge separation (SB-CS) and stabilized through non-covalent interactions. The photo-generated stable radical system is employed in anti-counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Ultrafast and Coherent Dynamics in a Solvent Switchable "Pink Box" Perylene Diimide Dimer.

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics and photovoltaic devices, supporting singlet fission and symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling is a strong function of dimer architecture. Recently, a macrocyclic PDI dimer was reported in which excitonic coupling could be turned on and off simply by changing the solvent. This presents a useful case where coupling is modified without synthetic changes to tune supramolecular structure. Here we present a detailed study of solvent dependent excited state dynamics in this dimer by means of coherent multidimensional spectroscopy. Spectral analysis resolves the different coupling strengths, which are consistent with solvent dependent changes in dimer conformation. The strongly coupled conformer forms an excimer within 300 fs. The low-frequency Raman active modes recovered from two-dimensional electronic spectra reveal frequencies characteristic of exciton coupling. These are assigned to modes modulating the coupling from the corresponding DFT calculations. Further analysis reveals a time dependent frequency during excimer formation. Analysis of two-dimensional "beatmaps" reveals features in the coupled dimer which are not predicted by the displaced harmonic oscillator model and are assigned to vibronic coupling.

Ultrafast and Coherent Dynamics in a Solvent Switchable “Pink Box” Perylene Diimide Dimer

AbstractPerylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics and photovoltaic devices, supporting singlet fission and symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling is a strong function of dimer architecture. Recently, a macrocyclic PDI dimer was reported in which excitonic coupling could be turned on and off simply by changing the solvent. This presents a useful case where coupling is modified without synthetic changes to tune supramolecular structure. Here we present a detailed study of solvent dependent excited state dynamics in this dimer by means of coherent multidimensional spectroscopy. Spectral analysis resolves the different coupling strengths, which are consistent with solvent dependent changes in dimer conformation. The strongly coupled conformer forms an excimer within 300 fs. The low‐frequency Raman active modes recovered from two‐dimensional electronic spectra reveal frequencies characteristic of exciton coupling. These are assigned to modes modulating the coupling from the corresponding DFT calculations. Further analysis reveals a time dependent frequency during excimer formation. Analysis of two‐dimensional “beatmaps” reveals features in the coupled dimer which are not predicted by the displaced harmonic oscillator model and are assigned to vibronic coupling.

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers.

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1'-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3',5'-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Symmetry Breaking Charge Separation in Far-Red Absorbing Bisstyryl-Bodipy Dimers

Symmetry breaking charge transfer is one of the important photo-events occurring in photosynthetic reaction centers that is responsible for initiating electron transfer leading to a long-lived charge-separated state and has been successfully employed in light-to-electricity converting optoelectronic devices. Here, we report the synthesis of far-red absorbing and emitting BODIPY-dimer to undergo symmetry-breaking charge transfer leading to charge-separated states of appreciable lifetimes in polar solvents. Compared to its monomer analog, both steady-state and time-resolved fluorescence originating from the S1 state of the dimer revealed quenching which increased with an increase in solvent polarity. The electrostatic potential map from DFT and the time-dependent DFT calculations suggested the existence of a quadrupolar type charge transfer state in polar solvents, and the singlet excited state to be involved in the charge separation process. The electrochemically determined redox gap to be smaller than the energy of the S1 state supporting thermodynamic feasibility of the envisioned symmetry-breaking charge transfer and separation. The spectrum of the charge-separated state arrived from spectroelectrochemical studies, revealing diagnostic peaks helpful for transient spectral interpretation. Finally, ultrafast transient pump-probe spectroscopy provided conclusive evidence of diabatic charge separation in polar solvents by far-red pulsed laser light irradiation. The measured lifetime of the final charge-separated states was found to be 165 ps in dichlorobenzene, 140 ps in benzonitrile, and 43 ps in dimethyl sulfoxide, revealing their significance in light energy harvesting, especially from the less-explored far-red region.

Manipulating symmetry-breaking charge separation employing molecular recognition

Manipulating symmetry-breaking charge separation employing molecular recognition

Aggregation-Driven Photoinduced α-C(sp3)-H Bond Hydroxylation/C(sp3)-C(sp3) Coupling of Boron Dipyrromethene Dye in Water Reported by Near-Infrared Emission.

Molecular aggregation is a powerful tool for tuning advanced materials' photophysical and electronic properties. Here we present a novel potential for the aqueous-solvated aggregated state of boron dipyrromethene (BODIPY) to facilitate phototransformations otherwise achievable only under harsh chemical conditions. We show that the photoinduced symmetry-breaking charge separation state can itself initiate catalyst-free redox chemistry, leading to selective α-C(sp3)-H bond activation/Csp3-Csp3 coupling on the BODIPY backbone. The photoproduction progress was tracked by monitoring the evolution of the strong Stokes-shifted near-infrared emission, resulting from selective self-assembly of the terminal heterodimeric photoproduct into well-ordered J-aggregates, as revealed by X-ray structural analysis. These findings provide a facile and green route to further explore the promising frontier of packing-triggered selective photoconversions via supramolecular engineering.

Symmetry-Breaking Charge Separation Mediated Triplet Population in a Perylenediimide Trimer at the Single-Molecule Level.

Herein, we demonstrate triplet excited-state population in a conformationally rigid perylenediimide trimer (PDI-T) via intramolecular symmetry-breaking charge separation (SB-CS) at the single-molecule level. The single-molecule fluorescence intensity trajectories of PDI-T in nonpolar polystyrene matrix (ε = 2.60) exhibit prolonged fluorescence with infrequent dark states, representing the triplet and/or the charge transfer states. In contrast, in a poly(vinyl alcohol) matrix (ε = 7.80), erratic blinking dynamics resulting in low photon counts were observed, corroborating the feasibility of charge separation in a polar environment. In agreement with the single-molecule measurements, transient absorption spectroscopy of PDI-T reveals ultrafast SB-CS (τCS < 5 ps) in polar tetrahydrofuran (ε = 7.58) and acetone (ε = 20.70), with the population of the triplet excited-state through charge recombination. The current investigation shows the utility of rigid and weakly coupled molecular constructs in controlling triplet generation and SB-CS for potential applications in optoelectronic devices.

Symmetry-breaking charge separation in a null-excitonic 3-dimensional rigid nonconjugated trimer.

Photoinduced symmetry-breaking charge separation (SB-CS) has been extensively observed in various oligomers and aggregates, which holds great potential for robust artificial solar energy conversion systems. It attaches great importance to the precise manipulation of interchromophore electronic coupling in realizing efficient SB-CS. The emerging studies on SB-CS suggested that it could be realized in null-excitonic aggregates, and a long-lived SB-CS state was observed, which offers an advanced platform and has gathered immense attention in the SB-CS field. Here, we unveiled the null-exciton coupling induced ultrafast SB-CS in a rigid polycyclic aromatic hydrocarbon framework, triperyleno[3,3,3]propellane triimides (TPPTI), in which three chromophores were attached through a nonconjugated bridge. Through a combination of theoretical calculations and steady-state absorption results, we demonstrated that this nonconjugated TPPTI possesses negligible exciton coupling. Increased solvent polarity was found to significantly enhance state mixing between local excited and charge transfer states. Using transient absorption spectroscopy, ultrafast SB-CS was observed in highly polar dimethylformamide, facilitated by a selective hole-transfer coupling and a favorable charge separation free energy (ΔGCS). Additionally, the rate ratio between SB-CS and charge recombination was at least high to 1800 in dimethylformamide. This investigation provides profound insights into the role of null-exciton coupling in dominating ultrafast SB-CS in multichromophoric systems.

Controlling Symmetry-Breaking Charge Separation in Pyrene Bichromophores.

So far, symmetry-breaking charge separation (SB-CS) has been observed with a limited number of chromophores and is usually inhibited by the formation of an excimer. We show here that thanks to fine-tuning of the interchromophore coupling via structural control, SB-CS can be operative with pyrene, despite its high propensity to form an excimer. This is realized with a bichromophoric system consisting of two pyrenes attached to a crown ether macrocycle, which can bind cations of different sizes. By combining stationary and time-resolved spectroscopy together with molecular dynamics simulations, we demonstrate that the excited-state dynamics can be totally changed depending on the binding cation. Whereas strong coupling leads to rapid excimer formation, too weak coupling results in noninteracting chromophores. However, intermediate coupling, achieved upon binding of Mg2+, allows for SB-CS to be operative.

Competitive Charge Separation Pathways in a Flexible Molecular Folda-Dimer.

We report the photophysical properties of a molecular folda-dimer system PDI-AnEt2-PDI, where the electron-donating N,N-diethylaniline (AnEt2) moiety bridges two electron-accepting perylene diimide (PDI) chromophores. The conformationally flexible PDI-AnEt2-PDI adopts either an open (two PDIs far apart) or folded (two PDIs within π-stacking distance) conformation, depending on the solvent environment. We characterized the photoinduced charge separation dynamics of both open and folded forms in solvents of varying polarity. The open form undergoes charge separation to give PDI•--AnEt2•+-PDI (Bridge electron transfer) independent of solvent polarity. The folded form exhibits two charge separation photoproducts, yielding both PDI•--AnEt2•+-PDI and PDI•--AnEt2-PDI•+, the latter of which is formed via symmetry-breaking charge separation (SBCS) between the two π-stacked PDI chromophores. Our results further indicate that the conformational flexibility of the folda-dimer leads to unexpected excimer formation in some open form conditions. In contrast, no excimer formation is observed in the folded form, indicating that this geometry preferentially yields the SBCS instead. Our results provide insight into how conformationally flexible folda-dimer systems can be designed and built to tune competitive photophysical pathways.

Symmetry-Breaking Charge Separation and Null Aggregates

Symmetry-Breaking Charge Separation and Null Aggregates

Ultrafast symmetry-breaking charge separation in Perylenemonoimide-embedded multichromophores: impact of regioisomerism.

Symmetry-breaking charge separation (SB-CS) has recently evolved as an emerging concept offering its potential to the latest generation of organic photovoltaics. However there are several concerns that need to be addressed to reach the state-of-the-art in SB-CS chemistry, for instance, the desirable molecular geometry, interchromophoric distance and extent of electronic coupling. To shed light on those features, it is reported herein, that ortho-functionalized perylene monoimide (PMI) constituted regioisomeric dimer and trimer derivatives with varied molecular twisting and electronic conjugation have been synthesized. In steady-state photophysical studies, all the dimers and trimer derivatives exhibit a larger bathochromic shift in the emission spectra and a significant reduction of fluorescence quantum yield in polar DMF. Among the series of multichromophores, ortho- and self-coupled dimers display the strikingly different optical feature of SB-CS with a very fast charge separation rate (τCS = 80.2 ps) upon photoexcitation in DMF, which is unveiled by femtosecond transient absorption (fs-TA) studies. The SB-CS for two dimers is well-supported by the formation of PMI˙+ and PMI˙- bands in the fs-TA spectra. Further analysis of fs-TA data revealed that, among the other multichromophores the trimer also exhibits a clear charge separation, whereas SB-CS signatures are less prominent, but can not be completely disregarded, for the meta- and para-dimers. Additionally, the charge separation dynamics of those above-mentioned PMI derivatives are devoid of a kinetically favorable excimer or triplet formation. The evidence of a profound charge transfer phenomenon in the ortho-dimer is characterized by density functional theory (DFT) calculations on excited state electronic structures. The excitonic communications in the excited state electronic arrangements unravel the key role of dihedral twisting in SB-CS. The thermodynamic feasibility of CS (ΔGCS) and activation barrier (ΔG≠) of the derivatives in DMF are established from the Rehm-Weller equation and Marcus's theory, respectively. This work is an in-depth study of the effect of mutual orientation of PMIs and regioisomerism in determining sustainable guidelines for using SB-CS.

Symmetry breaking charge transfer leading to charge separation in a far-red absorbing bisstyryl-BODIPY dimer.

Symmetry breaking charge transfer is one of the important photo-events occurring in photosynthetic reaction centers that is responsible for initiating electron transfer leading to a long-lived charge-separated state and has been successfully employed in light-to-electricity converting optoelectronic devices. In the present study, we report a newly synthesized, far-red absorbing and emitting BODIPY-dimer to undergo symmetry-breaking charge transfer leading to charge-separated states of appreciable lifetimes in polar solvents. Compared to its monomer analog, both steady-state and time-resolved fluorescence originating from the S1 state of the dimer revealed quenching which increased with an increase in solvent polarity. The electrostatic potential map from DFT and the time-dependent DFT calculations suggested the existence of a quadrupolar type charge transfer state in polar solvents, and the singlet excited state to be involved in the charge separation process. The electrochemically determined redox gap being smaller than the energy of the S1 state supported the thermodynamic feasibility of the envisioned symmetry-breaking charge transfer and separation. The spectrum of the charge-separated state arrived from spectroelectrochemical studies, revealing diagnostic peaks helpful for transient spectral interpretation. Finally, ultrafast transient pump-probe spectroscopy provided conclusive evidence of diabatic charge separation in polar solvents by far-red pulsed laser light irradiation. The measured lifetime of the final charge-separated states was found to be 165 ps in dichlorobenzene, 140 ps in benzonitrile, and 43 ps in dimethyl sulfoxide, revealing their significance in light energy harvesting, especially from the less-explored far-red region.

Ultrafast Charge Transfer Dynamics in a Slip-Stacked Donor-Acceptor-Acceptor System.

Photoexcitation of molecular electron donor and/or acceptor chromophore aggregates can greatly affect their charge-transfer dynamics. Excitonic coupling not only alters the energy landscape in the excited state but may also open new photophysical pathways, such as symmetry-breaking charge separation (SB-CS). Here, we investigate the impact of excitonic coupling on a covalent donor-acceptor-acceptor system comprising a perylene donor (Per) and two perylenediimide (PDI) acceptor chromophores in which the three components are π-stacked in a geometry that is slipped along their long axes (Per-PDI2). Following selective photoexcitation of PDI, femtosecond transient absorption data for Per-PDI2 is compared to that for the single-donor, single-acceptor Per-PDI system, and the PDI2 dimer, which both have the same interchromophore geometry as Per-PDI2. The data show that electron transfer from Per to the lower exciton state of the PDI dimer is slower than that of the single PDI acceptor system. This is due to the lower free energy of the reaction for charge separation because of the electronic stabilization afforded by the excitonic coupling between the PDIs. While PDI2 was shown previously to undergo ultrafast SB-CS, the strong π-π electronic interaction of Per with the adjacent PDI in Per-PDI2 breaks the electronic symmetry of the PDI dimer, resulting in the oxidation of Per rather than SB-CS. These results show that the electronic coupling between molecules designed to accept charges produced by SB-CS in molecular dimers and the chromophores comprising the dimer must be balanced to favor SB-CS.

Symmetry breaking charge transfer behaviour in D-A-D triad system by selective excitation

Multichromophoric D-A-D triads synthesized using perylenediimde (PDI) bonded with naphthalenediimide (NDI) units via aliphatic (Triad 1) or aromatic (Triad 2) linker is studied for symmetry breaking charge separation (SB-CS) by selective excitation of the NDI/PDI chromophores. NDI chromophore on excitation transfers electron to PDI chromophore and type of linker played crucial role in stability of generated CS state. Photoluminescence, time resolved fluorescense and transient absorption spectroscopy tools have been used to study the phenomenon. The optical as well as electrochemical study confirmed intramolecular electron transfer from NDI to PDI chromophore. Stable SB-CS state formation is directly resulted in increased open circuit voltage (Voc) of Triad 2 based organic solar cell devices. The selective excitation of chromophoric center and SB-CS in D-A-D type triad is the demand of present electronic device for the formation of long lived charge carrier.

Bimolecular photoinduced symmetry-breaking charge separation of perylene in solution

Photoinduced symmetry-breaking charge separation (SB-CS) results in the generation of charge carriers through electron transfer between two identical molecules, after photoexcitation of one of them. It is usually studied in systems where the two reacting moieties are covalently linked. Examples of photoinduced bimolecular SB-CS with organic molecules yielding free ions remain scarce due to solubility or aggregation issues at the high concentrations needed to study this diffusion-assisted process. Here we investigate the excited-state dynamics of perylene (Pe) at high concentrations in solvents of varying polarity. Transient absorption spectroscopy on the subnanosecond to microsecond timescales reveal that self-quenching of Pe in the lowest singlet excited state leads to excimer formation in all solvents used. Additionally, bimolecular SB-CS, resulting in the generation of free ions, occurs concurrently to excimer formation in polar media, with a relative efficiency that increases with the polarity of the solvent. Moreover, we show that SB-CS is most efficient in room-temperature ionic liquids due to a charge-shielding effect leading to a larger escape of ions and due to the high viscosity that disfavours excimer formation.Graphical abstract

Harvesting electrons and holes from photodriven symmetry-breaking charge separation within a perylenediimide photosynthetic model dimer.

Understanding how to utilize symmetry-breaking charge separation (SB-CS) offers a path toward increasingly efficient light-harvesting technologies. This process plays a central role in the first step of photosynthesis, in which the dimeric "special pair" of the photosynthetic reaction center enters a coherent SB-CS state after photoexcitation. Previous research on SB-CS in both biological and synthetic chromophore dimers has focused on increasing the efficiency of light-driven processes. In a chromophore dimer undergoing SB-CS, the energy of the radical ion pair product is nearly isoenergetic with that of the lowest excited singlet (S1) state of the dimer. This means that very little energy is lost from the absorbed photon. In principle, the relatively high energy electron and hole generated by SB-CS within the chromophore dimer can each be transferred to adjacent charge acceptors to extend the lifetime of the electron-hole pair, which can increase the efficiency of solar energy conversion. To investigate this possibility, we have designed a bis-perylenediimide cyclophane (mPDI2) covalently linked to a secondary electron donor, peri-xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of mPDI2, transient absorption spectroscopy shows that mPDI2 undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX•+-mPDI2-FNDI•- radical ion pair having a nearly 3 µs lifetime. This strategy has the potential to increase the efficiency of molecular systems for artificial photosynthesis and photovoltaics.

Spontaneous-Symmetry-Breaking Charge Separation Induced by Pseudo-Jahn-Teller Distortion in Organic Photovoltaic Material.

The driving force of charge separation in the initial photovoltaic conversion process is theoretically investigated using ITIC, a nonfullerene acceptor material for organic photovoltaic devices. The density functional theory calculations show that the pseudo-Jahn-Teller (PJT) distortion of the S1 excimer state induces spontaneous symmetry-breaking charge separation between the identical ITIC molecules even without the asymmetry of the surrounding environment. The strong PJT effect arises from the vibronic coupling between the pseudodegenerate S1 and S2 excited states with different irreducible representations (irreps), i.e., Au for S1 and Ag for S2, via the asymmetric vibrational mode with the Au irrep. The vibrational mode responsible for the spontaneous polarization, which is opposite in one ITIC monomer and the other, is the intramolecular C-C stretching vibration between the core IT and terminal IC units. These results suggest that controlling the PJT effect can improve the charge separation efficiency of the initial photovoltaic conversion process.