Excited State Charge Separation in an Azobenzene‐Bridged Perylenediimide Dimer – Effect of Photochemical Trans‐Cis Isomerization

Zink‐Lorre, Nathalie; Seetharaman, Sairaman; Gutiérrez‐Moreno, David; Fernández‐Lázaro, Fernando; Karr, Paul A.; D’Souza, Francis

doi:10.1002/chem.202102903

Cited by 5 publications

(4 citation statements)

References 37 publications

(23 reference statements)

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“…Minor structural changes can significantly affect the electron transfer and charge recombination ratio, making it difficult to compare with our results. Here, for the first time, we present the SB-CS of an α,α-ethylene bridge Bodipy dimer exhibiting clear J-type aggregation characteristics. , Other examples of molecular dimers in which the photophysical properties of molecular systems exhibiting SB-CS have been extensively studied previously, and our results are consistent with that prior work. ,− …”

Section: Resultssupporting

confidence: 87%

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model

Sandoval,

Gong,

Jiao

et al. 2023

J. Phys. Chem. A

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Bodipy is one of the most versatile and studied functional dyes due to its myriad applications and tunable spectral properties. One of the strategies to adjust their properties is the formation of Bodipy dimers and oligomers whose properties differ significantly from the corresponding monomer. Recently, we have developed a novel strategy for synthesizing α,α-ethylene-bridged Bodipy dimers; however, their excited-state dynamics was heretofore unknown. This work presents the ultrafast excited-state dynamics of a novel α,α-ethylene-bridge Bodipy dimer and its monomeric parent. The dimer's steady-state absorption and fluorescence suggest a Coulombic interaction between the monomeric units' transition dipole moments (TDMs), forming what is often termed a "J-dimer". The excited-state properties of the dimer were studied using molecular excitonic theory and time-dependent density functional theory (TD-DFT). We chose the M06 exchange−correlation functional (XCF) based on its ability to reproduce the experimental oscillator strength and resonance Raman spectra. Ultrafast laser spectroscopy reveals symmetry-breaking charge separation (SB-CS) in the dimer in polar solvents and the subsequent population of the charge-separated ion-pair state. The charge separation rate falls into the normal regime, while the charge recombination is in the inverted regime. Conversely, in nonpolar solvents, the charge separation is thermodynamically not feasible. In contrast, the monomer's excited-state dynamics shows no dependence on the solvent polarity. Furthermore, we found no evidence of significant structural rearrangement upon photoexcitation, regardless of the deactivation pathway. After an extensive analysis of the electronic transitions, we concluded that the solvent fluctuations in the local environment around the dimer create an asymmetry that drives and stabilizes the charge separation. This work sheds light on the charge-transfer process in this new set of molecular systems and how excited-state dynamics can be modeled by combining the experiment and theory.

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Section: Resultssupporting

confidence: 87%

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model

Sandoval,

Gong,

Jiao

et al. 2023

J. Phys. Chem. A

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“…[45][46][47][48] They are also widely used electron acceptors in multichromophoric systems and in electron-transporting devices. [49][50][51] The structures of the investigated compounds are shown in Figure 1. Here, bis-styryl entities carrying either terminal phenyl or triphenylamine (TPA) moieties on BODIPY are synthesized (abbreviated as PDI-BDP-diPh and PDI-BDP-diTPA in Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…It may be mentioned here that PDIs are of great significance in many scientific and technological advances including as a well‐known red pigment with outstanding stability, exhibiting high absorption in the 400–600 nm region, and fluorescence quantum yields close to one [45–48] . They are also widely used electron acceptors in multichromophoric systems and in electron‐transporting devices [49–51] …”

Section: Introductionmentioning

confidence: 99%

Panchromatic Light‐Capturing Bis‐styryl BODIPY‐Perylenediimide Donor‐Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer

Ileperuma,

Garcés‐Garcés,

Shao

et al. 2023

Chemistry A European J

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Two wide‐band capturing donor‐acceptor conjugates featuring bisstrylBODIPY and perylenediimide (PDI) have been newly synthesized and the occurrence of ultrafast excitation transfer from the 1PDI* to BODIPY, and a subsequent electron transfer from the 1BODIPY* to PDI has been demonstrated. Steady‐state fluorescence and excitation spectral recordings provided evidence of singlet‐singlet energy transfer in these dyads, and quenched fluorescence of bisstyrylBODIPY emission in the dyads suggested additional photo‐events. The electrostatic potential surfaces of the S1 and S2 states, derived from time‐dependent DFT calculations, supported excited charge transfer in these dyads. Spectroelectrochemical studies on one‐electron oxidized and one‐electron reduced dyads and the monomeric precursor compounds were also performed in a thin‐layer optical cell under corresponding applied potentials. From this study, both bisstrylBODIPY.+ and PDI.‐ were possible to spectrally characterize and were subsequently utilized in characterizing the electron transfer products. Finally, pump‐probe spectral studies were performed in dichlorobenzene under selective PDI and bisstyrylBODIPY excitation to secure energy and electron transfer evidence. The measured rate constants for energy transfer, kENT were in the range of 1011 s‐1 while the electron transfer rate constants, kET were in the range of 1010 s‐1 highlighting their potential use in solar energy harvesting and optoelectronic applications.

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“…[37][38][39][40] Besides the previously mentioned features, the extreme electronic conjugation along their large p-skeletons and high electron affinity has bestowed on them an additional attribute for better charge separation. [41][42][43] By exploiting those advantages, Wasielewski, Würthner and Kim, Xia, Hariharan and other groups have developed perylene diimide (PDI)-based multichromophoric systems exhibiting efficient charge separation and accomplishing long-lived charge-separated state via symmetry breaking. 36,[44][45][46] A myriad of the literature reveals that the PDI chromophore has been extensively employed for SB-CS, [47][48][49] but such a phenomenon on its monoimide analog (perylene monoimide, PMI) has barely been researched.…”

Section: Introductionmentioning

confidence: 99%

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

Roy,

Chawla,

Sharma

et al. 2024

Chem. Sci.

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Excited State Charge Separation in an Azobenzene‐Bridged Perylenediimide Dimer – Effect of Photochemical Trans‐Cis Isomerization

Abstract: Dedicated to Professor Tomás Torres on the occasion of his 70th birthday.

Cited by 5 publications

References 37 publications

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model

Panchromatic Light‐Capturing Bis‐styryl BODIPY‐Perylenediimide Donor‐Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer

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

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