Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

Aster, Alexander; Licari, Giuseppe; Zinna, Francesco; Brun, Elodie; Kumpulainen, Tatu; Tajkhorshid, Emad; Lacour, Jérôme; Vauthey, Eric

doi:10.1039/c9sc03913a

Cited by 66 publications

(99 citation statements)

References 83 publications

(107 reference statements)

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“…Over the past few years, there has been a growing interest for symmetry-breaking (SB) charge transfer processes occurring in multichromophoric systems and multipolar conjugated dyes. [1] One of them, symmetry-breaking charge separation, occurs between two identical chromophores, [2][3][4][5][6][7][8][9][10][11][12][13] and offers interesting perspectives for applications in photovoltaics and artificial photosynthesis. [14,15] Here, electronic excitation can initially be entirely localised on one of the chromophores.…”

Section: Introductionmentioning

confidence: 99%

Change of Quadrupole Moment upon Excitation and Symmetry Breaking in Multibranched Donor‐Acceptor Dyes

et al. 2020

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Upon photoexcitation, a majority of quadrupolar dyes, developed for large two‐photon absorption, undergo excited‐state symmetry breaking (ES‐SB) and behave as dipolar molecules. We investigate how the change of quadrupole moment upon S1←S0 excitation, ΔQ, influences the propensity of a dye to undergo ES‐SB using a series of molecules with a A‐π‐D‐π‐A motif where D is the exceptionally electron‐rich pyrrolo[3,2‐b]pyrrole and A are accepting groups. Tuning of ΔQ is achieved by appending a secondary acceptor group, A’, on both sides of the D core and ES‐SB is monitored using a combination of time‐resolved IR and broadband fluorescence spectroscopy. The results reveal a clear correlation between ΔQ and the tendency to undergo ES‐SB. When A is a stronger acceptor than A’, ES‐SB occurs already in non‐dipolar but quadrupolar solvents. When A and A’ are identical, ES‐SB is only partial even in highly dipolar solvents. When A is a weaker acceptor than A’, the orientation of ΔQ changes, ES‐SB is observed in dipolar solvents only and involves major redistribution of the excitation over the D‐π‐A and D‐A’ branches of the dye.

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Section: Introductionmentioning

confidence: 99%

Change of Quadrupole Moment upon Excitation and Symmetry Breaking in Multibranched Donor‐Acceptor Dyes

et al. 2020

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“…11 Macrocycles 1e and 1f used as reversible ratiometric luminescent switches and scaffolds to study targeted photophysical properties, respectively. 32,33 to ECD transitions cancelling each other. However, upon cation addition and binding, the overall number of conformations decreased and the novel conformationally-constrained geometries favored the inverted ECD signal(s) leading to the observed enhancement ( Fig.…”

Section: Effective Chiroptical Propertiesmentioning

confidence: 98%

“…It was demonstrated that the nature of the excited state varies greatly from an excimer to a symmetry-broken charge separated state depending on the conformational restrictions (cation binding) and the local environment. 33…”

Section: Luminescence Quenching Monitoringmentioning

confidence: 99%

From reactive carbenes to chiral polyether macrocycles in two steps – synthesis and applications made easy?

Homberg

Lacour

2020

Chem. Sci.

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“…The formation of excited charge transfer state depends on the mutual orientation and distance of the molecules. [35] For spatially separated excited charge transfer states, the oscillatory strength depends on certain degree of electronic wavefunction overlap. Besides, the intermolecular distance plays an important role, the degree of face-to face overlapping is also important for excitation of spatially separated charge transfer states.…”

Section: (D)mentioning

confidence: 99%

Effect of Bulky Functional Groups on Donor and Acceptor Interactions and their Photoluminescence Properties

et al. 2020

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Material designs that use donor and acceptor units are often found in organic optoelectronic devices. Molecular level insight into the interactions between donors and acceptors are crucial for understanding how such interactions can modify the optical properties of the organic optoelectronic materials. In this paper, tris(4-(tert-butyl)phenyl)amine (pTPA) was synthesized as a donor in order to compare with unmodified triphenylamine (TPA) in a donor-acceptor system by having 2,4,6-triphenyl-1,3,5-triazine (TRZ) as an acceptor. Dimerization of donors and acceptors occurred in solvent when the concentration of solute is high. At 0 K, using a polarizable continuum model, the nitrogen atom of TPA is found to stack on top of the center of triazine of TRZ, whereas such alignment is offset in pTPA and TRZ. We attributed such alignment in TPA-TRZ as the result of attractive interactions between partial localization of 2p z electrons at the nitrogen atom of TPA and the π deficiency of triazine in TPA-TRZ. By taking into account random motions of the solvent effect at 300 K in quantum molecular dynamics and classical molecular dynamics simulations to interpret the marked difference in emission spectra between TPA-TRZ and pTPA-TRZ, it was revealed that the attractive interaction between pTPA and TRZ in toluene is weaker than TPA and TRZ. Because of the weaker attractive interaction between pTPA and TRZ in toluene, the dimers adopted numerous ground state conformations resulting in broad emission bands superimposed with multiple small Gaussian peaks. This is in contrast to TPA-TRZ which has only one dominant dimer conformation. This study demonstrates that the strength of intermolecular interactions between donors and acceptors should be taken into consideration in designing supramolecular structures.

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Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

Abstract: Varying the structure of perylene-based dimers allows tuning the excited state from an excimer to a charge-separated state.

Cited by 66 publications

References 83 publications

Change of Quadrupole Moment upon Excitation and Symmetry Breaking in Multibranched Donor‐Acceptor Dyes

Change of Quadrupole Moment upon Excitation and Symmetry Breaking in Multibranched Donor‐Acceptor Dyes

From reactive carbenes to chiral polyether macrocycles in two steps – synthesis and applications made easy?

Effect of Bulky Functional Groups on Donor and Acceptor Interactions and their Photoluminescence Properties

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