On the Fine‐Tuning of the Excited‐State Intramolecular Proton Transfer (ESIPT) Process in 2‐(2′‐Hydroxybenzofuran)benzazole (HBBX) Dyes

Heyer, Elodie; Benelhadj, Karima; Budzák, Šimon; Jacquemin, Denis; Massue, Julien; Ulrich, Gilles

doi:10.1002/chem.201700299

Cited by 70 publications

(48 citation statements)

References 60 publications

(85 reference statements)

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“…Moreover, the molecules may also show the presence of multi-stage phototautomerization processes, ESIPT (excited state intramolecular proton transfer) [ 32 , 33 , 34 , 35 , 36 ]. The properties characterizing ESIPT molecules include dual fluorescence emission, a relatively significant Stokes shift, exceptional process dynamics, as well as high sensitivity of emission spectra to changing properties of the medium [ 37 , 38 , 39 , 40 ]. Additionally, Yamaguchi et al reported on quite non-typical ESIPT-related dual emission in compounds stabilized in their zwitterionic form in the excited state [ 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

ESIPT-Related Origin of Dual Fluorescence in the Selected Model 1,3,4-Thiadiazole Derivatives

et al. 2020

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In our previous work, we discussed the emergence of the dual fluorescence phenomenon in selected compounds from the group of 1,3,4-thiadiazoles. The results obtained in a number of experimental studies, supported by [TD]DFT calculations, clearly indicated that the phenomenon of dual fluorescence stemmed from an overlap of several factors, including the correct conformation of the analyzed molecule and, very significantly in this context, aggregation effects. Where those two conditions were met, we could observe the phenomenon of intermolecular charge transfer (CT) and the emergence of electronic states responsible for long wave emissions. However, in light of the new studies presented in this paper, we were able, for the first time, to provide a specific theory for the effect of dual fluorescence observed in the analyzed group of 1,3,4-thiadiazoles. We present the results of spectroscopic measurements conducted for two selected analogues from the 1,3,4-thiadiazole group, both in polar and non-polar solvents, which clearly evidence (as we have already suspected in the past, albeit have not shown in publications to date) the possibility of processes related to emission from the tautomer formed in the process of excited state intramolecular proton transfer, which is responsible for the long-wavelength emissions observed in the selected analogues. The presented results obtained with the use of UV-Vis, fluorescence (stationary and time-resolved), FTIR, and Raman spectroscopy, as well as from calculations of dipole moment changes between the ground and excited state with the use of two derivatives with different structures of the resorcylic system, corroborated our standing hypothesis. At the same time, they excluded the presence of ground state keto forms of the analyzed analogues unless necessitated by the structure of the molecule itself. In this case, aggregation factors enhance the observed effects related to the dual fluorescence of the analyzed compounds (by way of AIE—aggregated induced emissions).

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Section: Introductionmentioning

confidence: 99%

ESIPT-Related Origin of Dual Fluorescence in the Selected Model 1,3,4-Thiadiazole Derivatives

et al. 2020

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“…The excited state intramolecular proton transfer (ESIPT) process is the simplest photochemical reaction (Scheme ). It includes photoexcitation of a molecule in the enol form, S 0 e →S 1 e , a fast enol‐to‐keto S 1 e →S 1 k ESIPT ( k ESIPT ≈10 12 s −1 ) and, finally, the S 1 k →S 0 k emission in the keto form followed by fast ground state intramolecular proton transfer (GSIPT), S 0 k →S 0 e …”

Section: Methodsmentioning

confidence: 99%

Excitation‐Wavelength‐Dependent Emission and Delayed Fluorescence in a Proton‐Transfer System

Berezin

Vinogradova

Krivopalov

et al. 2018

Chemistry A European J

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Manipulating the relaxation pathways of excited states and understanding mechanisms of photochemical reactions present important challenges in chemistry. Here we report a unique zinc(II) complex exhibiting unprecedented interplay between the excitation-wavelength-dependent emission, thermally activated delayed fluorescence (TADF) and excited state intramolecular proton transfer (ESIPT). The ESIPT process in the complex is favoured by a short intramolecular OH⋅⋅⋅N hydrogen bond. Synergy between the excitation-wavelength-dependent emission and ESIPT arises due to heavy zinc atom favouring intersystem crossing (isc). Reverse intersystem crossing (risc) and TADF are favoured by a narrow singlet-triplet gap, ΔE ≈10 kJ mol . These results provide the first insight into how a proton-transfer system can be modified to show a synergy between the excitation-wavelength-dependent emission, ESIPT and TADF. This strategy offers new perspectives for designing ESIPT and TADF emitters exhibiting tunable excitation-wavelength-dependent luminescence.

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“…Further studies are thus needed to investigate the relationship between newly identified environmental toxicants such as particulate matter (PM2.5) and polycyclic aromatic hydrocarbons (PAH), which were recently suspected to have a negative impact on fetal development [214]. In addition to prenatal environmental toxicant exposure, a recent review focused on neurodevelopmental disorders, particularly ASD, ADHD, and schizophrenia, and described that the susceptibility of neurodevelopmental disorders to toxicant exposure is not limited to the gestational period but extends into the postnatal period [215]. As described earlier, epigenetic mechanisms, especially DNA methylation, are assumed to be the mechanism underlying the effect of toxicants on neurodevelopment.…”

Section: Conclusion and Perspectivementioning

confidence: 99%

Neurodevelopmental Disorders and Environmental Toxicants: Epigenetics as an Underlying Mechanism

Tran

Miyake

2017

International Journal of Genomics

116

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The increasing prevalence of neurodevelopmental disorders, especially autism spectrum disorders (ASD) and attention deficit hyperactivity disorder (ADHD), calls for more research into the identification of etiologic and risk factors. The Developmental Origin of Health and Disease (DOHaD) hypothesizes that the environment during fetal and childhood development affects the risk for many chronic diseases in later stages of life, including neurodevelopmental disorders. Epigenetics, a term describing mechanisms that cause changes in the chromosome state without affecting DNA sequences, is suggested to be the underlying mechanism, according to the DOHaD hypothesis. Moreover, many neurodevelopmental disorders are also related to epigenetic abnormalities. Experimental and epidemiological studies suggest that exposure to prenatal environmental toxicants is associated with neurodevelopmental disorders. In addition, there is also evidence that environmental toxicants can result in epigenetic alterations, notably DNA methylation. In this review, we first focus on the relationship between neurodevelopmental disorders and environmental toxicants, in particular maternal smoking, plastic-derived chemicals (bisphenol A and phthalates), persistent organic pollutants, and heavy metals. We then review studies showing the epigenetic effects of those environmental factors in humans that may affect normal neurodevelopment.

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On the Fine‐Tuning of the Excited‐State Intramolecular Proton Transfer (ESIPT) Process in 2‐(2′‐Hydroxybenzofuran)benzazole (HBBX) Dyes

Cited by 70 publications

References 60 publications

ESIPT-Related Origin of Dual Fluorescence in the Selected Model 1,3,4-Thiadiazole Derivatives

ESIPT-Related Origin of Dual Fluorescence in the Selected Model 1,3,4-Thiadiazole Derivatives

Excitation‐Wavelength‐Dependent Emission and Delayed Fluorescence in a Proton‐Transfer System

Neurodevelopmental Disorders and Environmental Toxicants: Epigenetics as an Underlying Mechanism

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