How does tetraphenylethylene relax from its excited states?

Prlj, Antonio; Došlić, Nađa; Corminbœuf, Clémence

doi:10.1039/c5cp04546k

Cited by 95 publications

(105 citation statements)

References 42 publications

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“…This is consistent with the results from a recent TSH dynamics study of the parent TPE molecule at the TDA-TDDFT level, in which the vast majority of the trajectories led to photocyclization. 18 …”

Section: Discussionmentioning

confidence: 99%

“…However, according to the recent TDA-TDDFT work on the parent TPE molecule, the cyclic S 0 form is photochemically unstable; upon photoexcitation, it will undergo the reverse ring-opening reaction back to TPE in an ultrafast photoinduced process. 18 Its spectroscopic detection is thus expected to be very challenging experimentally.…”

Section: Discussionmentioning

confidence: 99%

“…18 During the 1.5 ps simulation, only 3 out of 60 computed trajectories decayed to the ground state via the ethylenic twist pathway (E/Z photoisomerization), while 45 relaxed via photocyclization to ground-state 9,10-diphenyl-4 a ,4 b -dihydrophenanthrene and 12 remained in the excited state. 18 …”

Section: Introductionmentioning

confidence: 98%

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Excited-State Decay Paths in Tetraphenylethene Derivatives

et al. 2017

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The photophysical properties of tetraphenylethene (TPE) compounds may differ widely depending on the substitution pattern, for example, with regard to the fluorescence quantum yield ϕf and the propensity to exhibit aggregation-induced emission (AIE). We report combined electronic structure calculations and nonadiabatic dynamics simulations to study the excited-state decay mechanisms of two TPE derivatives with four methyl substituents, either in the meta position (TPE-4mM, ϕf = 0.1%) or in the ortho position (TPE-4oM, ϕf = 64.3%). In both cases, two excited-state decay pathways may be relevant, namely, photoisomerization around the central ethylenic double bond and photocyclization involving two adjacent phenyl rings. In TPE-4mM, the barrierless S1 cyclization is favored; it is responsible for the ultralow fluorescence quantum yield observed experimentally. In TPE-4oM, both the S1 photocyclization and photoisomerization paths are blocked by non-negligible barriers, and fluorescence is thus feasible. Nonadiabatic dynamics simulations with more than 1000 surface hopping trajectories show ultrafast cyclization upon photoexcitation of TPE-4mM, whereas TPE-4oM remains unreactive during the 1 ps simulations. We discuss the chances for spectroscopic detection of the postulated cyclic photoproduct of TPE-4mM and the relevance of our findings for the AIE process.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Excited-State Decay Paths in Tetraphenylethene Derivatives

et al. 2017

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“…In π-conjugated systems, these states are of great relevance for both absorption and emission properties, 4−7 and they play a major role in determining available decay channels. 8−11 …”

Section: Introductionmentioning

confidence: 99%

Low-Lying ππ* States of Heteroaromatic Molecules: A Challenge for Excited State Methods

Prlj

Sandoval‐Salinas

Casanova

et al. 2016

J. Chem. Theory Comput.

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The description of low-lying ππ* states of linear acenes by standard electronic structure methods is known to be challenging. Here, we broaden the framework of this problem by considering a set of fused heteroaromatic rings and demonstrate that standard electronic structure methods do not provide a balanced description of the two (typically) lowest singlet state (La and Lb) excitations. While the Lb state is highly sensitive to correlation effects, La suffers from the same drawbacks as charge transfer excitations. We show that the comparison between CIS/CIS(D) can serve as a diagnostic for detecting the two problematic excited states. Standard TD-DFT and even its spin-flip variant lead to inaccurate excitation energies and interstate gaps, with only a double hybrid functional performing somewhat better. The complication inherent to a balanced description of these states is so important that even CC2 and ADC(2) do not necessarily match the ADC(3) reference.

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“…[9] To guide the design of novel AIE organicf unctionalm aterials properly,t he mechanism of AIE is in need of furtheri nvestigation in details. [12] In this work, we choose 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carbaldehyde (P 4 TA), at etraphenylethylene (TPE) de-The case that aggregation has al arge influence on the structure andf luorescent properties of 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carbaldehyde (P 4 TA)i si nvestigated in detail herein by employing quantum mechanics and molecular mechanics. Wu and his coworkers reported quantitative calculation of fluorescence quantum efficiency for the molecular aggregation state in solution through combining quantum mechanics and molecular mechanics (QM/MM)c oupled with correlation function formalism for the internal conversion (IC), considering Duschinsky rotation effect relatedt ol ow-frequency phenyl ring twisting.…”

Section: Introductionmentioning

confidence: 99%

Influence of Aggregation on the Structure and Fluorescent Properties of a Tetraphenylethylene Derivative: a Theoretical Study

Duan

Jin

et al. 2017

ChemPhysChem

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The case that aggregation has a large influence on the structure and fluorescent properties of 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carbaldehyde (P TA) is investigated in detail herein by employing quantum mechanics and molecular mechanics. Besides the isolated molecule, the aggregated molecule in water and in the crystalline state was studied by focusing on the comparison of photoelectronic properties, including the geometrical and electronic structures at ground and excited states, emission and internal conversation properties. For the aggregation state, the intermolecular interaction was used to explain the difference in structure, emission color and intensity of different polymorphs. The noticeable contribution from low-frequency region, corresponding to the four phenyl rings twisting vibration, to the Huang-Rhys factor and reorganization energy, as well as the possible potential energy surface crossing between S and S states for isolated molecules was considered as the reason of its aggregation-induced emission (AIE) performance. Importantly, the aggregation process in water simulated at the same time helps us to have a deeper understanding of the AIE behavior of P TA, which also provides another perspective to explore the AIE phenomenon in theory.

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How does tetraphenylethylene relax from its excited states?

Cited by 95 publications

References 42 publications

Excited-State Decay Paths in Tetraphenylethene Derivatives

Excited-State Decay Paths in Tetraphenylethene Derivatives

Low-Lying ππ* States of Heteroaromatic Molecules: A Challenge for Excited State Methods

Influence of Aggregation on the Structure and Fluorescent Properties of a Tetraphenylethylene Derivative: a Theoretical Study

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