Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer.

The photophysical properties of 4-aminonaphthalene-1,8-imide-based derivatives, bis-ANI, consisting of two naphthalimide (NI) units linked by a butylamine bridge and its monomer ANI have been intensively investigated by steady-state and transient spectroscopy combined with quantum chemical calculations. The excited state relaxation dynamics of the two molecules are studied in three solvents of varying polarity - from hexane to tetrahydrofuran to acetone. A strong reduction in the fluorescence quantum yields and larger red shifts of the emission spectra are observed when going from the monomer ANI to dimer bis-ANI with increasing solvent polarity. It is found that the presence of the central amino linker in bis-ANI facilitates the formation of an asymmetric CS state between the ANI and NI moieties in bis-ANI, where NI˙- is the dominant radical anion unit after CS, evidenced by the femtosecond transient absorption measurements and spectroelectrochemistry in polar solvents. Femtosecond transient absorption spectra and quantum chemical calculations reveal the conformational change after the formation of the symmetry-breaking charge separation (SBCS) state upon photoexcitation, while a near-orthogonal structure in the excited state of bis-ANI retards charge recombination. In addition, it is evidenced that the rate of SBCS can be tuned by changing the different polar solvents.

Bridge-Length- and Solvent-Dependent Charge Separation and Recombination Processes in Donor-Bridge-Acceptor Molecules.

The photoinduced intramolecular charge separation (CS) and charge recombination (CR) phenomena in a series of donor-bridge-acceptor (D-B-A) molecules are intensively investigated as a means of understanding electron transport through the π-B. Pyrene (Pyr) and triarylamine (TAA) moieties connected via phenylene Bs of various lengths are studied because their CS and CR behaviors can be readily monitored in real time by femtosecond transient absorption (fs-TA) spectroscopy. By combining the steady-state and fs-TA spectroscopic measurements in a variety of solvents together with chemical calculations, the parameters that govern the CS behaviors of these dyads were obtained, such as the solvent effects on free energy and the B-length-dependent electronic coupling (VDA) between D and A. We observed the sharp switch of the CS behavior with the increase of the solvent polarity and B-linker lengths. Furthermore, in the case of the shortest distance between D and A when the electron coupling is sufficiently large, we observed that the CS phenomenon occurs even in low-polar solvents. Upon increasing the length of B, CS occurs only in strong polar solvents. The distance-dependent decay constant of the CS rate is determined as ∼0.53 Å-1, indicating that CS is governed by superexchange tunneling interactions. The CS rate constants are also approximately estimated using Marcus electron transfer theory, and the results imply that the VDA value is the key factor dominating the CS rate, while the facile rotation of the phenylene B is important for modulating the lifetime of the charge-separated state in these D-B-A dyads. These results shed light on the practical strategy for obtaining a high CS efficiency with a long-lived CS state in TAA-B-Pyr derivatives.

Direct Tracking Excited-State Intramolecular Charge Redistribution of Acceptor-Donor-Acceptor Molecule by Means of Femtosecond Stimulated Raman Spectroscopy.

Symmetric quadrupolar molecules generally exhibit apolar ground states and dipolar excited states in a polar environment, which is explained by the excited state evolution from initial charge delocalization over all molecules to localization on one branch of the molecules after a femtosecond pulse excitation. However, direct observation of excited-state charge redistribution (delocalization/localization) is hardly accessible. Here, the intramolecular charge delocalization/localization character of a newly synthesized acceptor-donor-acceptor molecule (ADA) has been intensively investigated by femtosecond stimulated Raman scattering (FSRS) together with femtosecond transient absorption (fs-TA) spectroscopy. By tracking the excited state Raman spectra of the specific alkynyl (-C≡C-) bonds at each branch of ADA, we found that the nature of the relaxed S1 state is strongly governed by solvent polarity: symmetric delocalized intramolecular charge transfer (ICT) characters occurred in apolar solvent, whereas the asymmetric localized ICT characters appeared in polar solvent because of solvation. The solvation dynamics of ADA extracted from fs-TA is consistent with the time constants obtained by FSRS, but the FSRS clearly tracks the excited state intramolecular charge transfer delocalization/localization.

Excited-State Symmetry-Breaking Charge Separation Dynamics in Multibranched Perylene Diimide Molecules.

As one of the most promising nonfullerene acceptors for organic photovoltaics, perylene diimide (PDI)-based multibranched molecules with twisted or three-dimensional (3D) geometric structures have been developed, which effectively increase the power conversion efficiency (PCE) of organic solar cells. Understanding the structure-property relationships in multichromophoric molecular architectures at molecular and ultrafast time levels is a crucial step in establishing new design principles in organic electronic materials. For this, photodriven excited-state symmetry-breaking charge separation (SB-CS) of PDI-based multichromophoric acceptors has been proposed to improve the PCE by reducing the self-aggregation of the planar PDI monomer. Herein, we investigated the intramolecular excited-state SB-CS and charge recombination (CR) dynamics of two symmetric phenyl-methane-based PDI derivatives, a twist dimer PM-PDI2 (phenyl-methane-based PDI dimer) and a 3D configuration tetramer PM-PDI4 (phenyl-methane-based PDI tetramer), in different solvents using ultrafast femtosecond transient absorption (fs-TA) spectroscopy and quantum chemical calculations. The quantum chemical calculations and steady-state spectra show that the two PDI derivatives undergo conformational changes upon excitation, leading to their emission states that have the characteristics of partial charge-transfer (CT) exciton in all solvents. Based on the evolution of the fs-TA data, it is observed that the evolution from the CT state to SB-CS state is disfavored in a weak polar solvent, whereas clear SB-CS spectroscopic signatures of cationic and anionic PDI are observed in polar solvents. Faster CS and slower CR processes of PM-PDI4 are observed in comparison to those of PM-PDI2. The crowded space in the 3D structure shortens the distance between the branches, leading to a stronger electronic coupling at the lowest excited state and a larger negative Gibbs free energy change of PM-PDI4 relative to that of PM-PDI2, which benefits the charge separation among PDI units in PM-PDI4. Besides, the 3D structure of PM-PDI4 also restricts rotation to a surface crossing region between the excited state and ground state, thus inhibiting nonradiative CR process and increasing the CS state lifetime. Our results suggest that the kinetics of CS and CR processes are strongly related to the molecular geometric structure, and the excited-state symmetry breaking in the 3D structure acceptor has superior photogenerated charge and photovoltaic properties from the perspective of ultrafast dynamics.

Electron-donating strength dependent symmetry breaking charge transfer dynamics of quadrupolar molecules.

The excited state symmetry breaking charge transfer (SBCT) dynamics of two diacetylide-triphenylamine (DATPA) derivatives with different electron-donating abilities are investigated by femtosecond transient absorption and fluorescence spectroscopy. By tracking the evolution of the excited states by transient absorption spectra and the kinetics of the instantaneous emission dipole moments obtained from transient fluorescence spectroscopy, it is found that, in nonpolar solvent, the relaxed S1 state is quadrupolar with little change of emission dipole moments for the two molecules within 30 ps, whereas in polar solvent, the quadrupolar state evolves to a symmetry broken S1 state, in which, the emission dipole moment exhibits a fast reduction in the first few picoseconds. The larger reduction in emission transition dipole moment for the molecule with stronger electron-donating methoxy groups indicates a larger extent of symmetry breaking compared with the one with weak electron-donating methyl groups. Consequently, we revealed that the magnitude of symmetry breaking can be tuned by changing the electron-donors in quadrupolar molecules.

Bridge-Mediated Charge Separation in Isomeric N-Annulated Perylene Diimide Dimers.

The possibility and rate of charge separation (CS) in donor-bridge-acceptor molecules mainly depend on two factors: electronic coupling and solvent effects. The question of how CS occurred in two identical chromophores is fundamental, as it is particularly interesting for potential molecular electronics applications and the photosynthetic reaction centers (RCs). Conjugated bridge definitely plays a crucial role in electronic coupling. To determine the bridge-mediated charge separation dynamics between the two identical chromophores, the isomeric N-annulated perylene diimide dimers (para-BDNP and meta-BDNP) with different conjugated bridge structures have been comparatively investigated in different solvents using femtosecond transient absorption spectra (fs-TA). It is found that the charge separation is disfavored in weak polar solvent, whereas direct spectroscopic signatures of radicals are observed in polar solvents, and the rate of charge separation increases as the solvent polarity increasing. To our surprise, the rate of charge separation in m-BDNP is more than an order of magnitude slower than that in p-BDNP, although there is a larger negative ΔGCS in m-BDNP. The slow CS rate that occurred in m-BDNP mainly results from the intrinsic destructive interference of the wave function through the meta-substituted bridge. The roles of solvent effects in free energy and electronic coupling for charge separation are further identified with quantum calculations.

Intramolecular charge transfer and solvation dynamics of push-pull dyes with different π-conjugated linkers.

The solvation-dependent excited state dynamics of two push-pull fluorophores with donor-π-acceptor (D-π-A) structures were investigated using steady-state and ultrafast transient absorption (TA) spectroscopy, backed by theoretical calculations. Identical D and A groups were present in both dyes, which differed only in the structure of their central π-conjugated linkers. Dye 1 features a p-phenylenediethynyl linker, while dye 2 contains a 2,5-diethynylthiophene linker. From the steady-state spectra, no appreciable shifts in absorption bands were observed, whereas large red-shifts in emission were seen with increasing solvent polarity, which indicated that the excited states were more polar than the ground state. Theoretical calculations support charge transfer from the triphenylamine (TPA) donor to the pentafluorosulfanyl (SF5) acceptor viaπ-conjugated linkers to form an intramolecular charge transfer (ICT) state. TA spectra revealed that a solvation-stabilized conformationally relaxed intramolecular charge transfer (ICT') state was formed in polar solvents, but only an ICT state was observed in nonpolar solvent. The SE band was quenched within 1 ps in high-polarity solvent, which corresponds to the low fluorescence quantum yield. It can be concluded that the dye with the p-phenylenediethynyl π-linker (i.e., dye 1) exhibits a larger degree of ICT than the thiophene analogue (i.e., dye 2). These findings demonstrate how solvation can fine-tune the photophysical properties of push-pull dyes, and this study highlights the importance of π-conjugated linkers in the excited state ICT process.