Mechanism of Fluorescence Switching in One ESIPT-Based Al<sup>3+</sup> Probe

Budzák, Šimon; Jacquemin, Denis

doi:10.1021/acs.jpcb.6b04474

Cited by 36 publications

(10 citation statements)

References 56 publications

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“…However, in the light of our new, previously unpublished results related to the emergence of dual fluorescence emission, as observed in non-polar solvents such as, e.g., chloroform ( Figure 2 A) or toluene ( Figure S2 in SM ), we can now positively associate the effect of dual fluorescence observed in this group of analogues with the process of excited state intramolecular proton transfer. Similar systems are often mentioned in literature reports where the cause of the dual fluorescence effect is identified as ESIPT [ 46 , 47 , 48 , 49 , 50 , 51 ]. Long-wavelength emission is often observed in molecules which have the ability to form an intramolecular hydrogen bond between the proton donor and acceptor ( Scheme 2 B).…”

Section: Resultsmentioning

confidence: 60%

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: Resultsmentioning

confidence: 60%

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

et al. 2020

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“…Thus, Al 3+ has been detected in the low-polar solvent, whereas Zn 2+ has been detected in the high-polar solvent. In addition, an ESIPT stiffening mechanism is responsible for the strong fluorescence turn-on after formation of complexes between Al 3+ /Zn 2+ cations and the dehydrogenated Schiff base. ,, Thus, by combining the above-mentioned mechanisms, the plausible recognition and sensing modes for detection of Al 3+ and Zn 2+ have been drawn as follows (Scheme ). ,, …”

Section: Resultsmentioning

confidence: 99%

Solvent-Regulated Fluorimetric Differentiation of Al³⁺ and Zn²⁺ Using an AIE-Active Single Sensor

Das

Dolai²,

Dhara

et al. 2021

J. Phys. Chem. A

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The absence of d-orbital electrons or presence of full-filled d-orbital electrons in metal ions is a well-known Achilles' heel problem for the detection of these metal ions by a simple UV-visible study. For this reason, detection of metal ions such as Al 3+ with no d-orbital electrons or Zn 2+ with filled d-orbital electrons is a challenging task. Herein, we report a 2-naphthol-based fluorescent probe [1-((E)-((E)-(5-bromo-2-hydroxybenzylidene)hydrazono)methyl)naphthalen-2-ol] (H 2 L) that has been used to sense and discriminate Al 3+ and Zn 2+ via solvent regulation. The probe exhibits excellent selectivity and swift sensitivity toward Al 3+ in MeOH− water (9:1, v/v) and toward Zn 2+ in dimethyl sulfoxide (DMSO)−water (9:1, v/v) among various metal ions. The respective detection limit is found to be 9.78 and 3.65 μM. The sensing mechanism is attributed to multiple processes, viz., the inhibition of photo-induced electron transfer (PET) along with the introduction of chelation-enhanced emission (CHEF) and excited-state intramolecular proton transfer (ESIPT) inhibition, which are experimentally well verified by UV−vis absorption spectroscopy, emission spectroscopy, and NMR spectroscopy. The probe shows aggregation-induced emissive (AIE) response in ≥70% aqueous media as well as in the solid state. The experimental results are well corroborated by time-resolved photoluminescence (TRPL) and density functional theory (DFT) calculations. An advanced-level OR-AND-NOT logic gate has been constructed from a different chemical combinational input and emission output. The reversible recognition of both Al 3+ in MeOH−water (9:1, v/v) and Zn 2+ in DMSO−water (9:1, v/v) is also ascertained in the presence of Na 2 EDTA, enabling the construction of a molecular memory device. The probe H 2 L also detects intracellular Al 3+ /Zn 2+ ions in Hela cells. Altogether, our fundamental findings will pave the way for designing and synthesis of unique chemosensors that could be used for cell imaging studies as well as constructing molecular logic gates.

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“…As the previous reports, [60,61,[63][64][65][66][67] SHs acting as an O^N^O terdentate ligand can coordinate with many metal ions, and thus they can be used as metal ion probes. Among these SHs, Naph-SH-C 3 , SH-C 3 , and Naph-SH-Ph exhibit the best performances for detecting Mg 2+ , as shown in Table S2.…”

Section: Ion Probe Propertiesmentioning

confidence: 94%

“…Can the intermolecular hydrogen bonds improve the AIE properties of salicylaldehyde hydrazides (SHs, Figure 2)? In the literature, however, there are only limited examples of non-emissive SHs that were used as turn-on fluorescence probers for detecting ions, such as Mg 2+ , [60,61] Zn 2+ , [60,62] Al 3+ , [62][63][64][65][66][67] F  , [68] and CN  , [69,70] and showed polar solvent-induced fluorescence. [71] Herein, we firstly reported a series of simple and soft SH materials (41 samples, Figure 2) that exhibit multiple intramolecular and intermolecular hydrogen bonds promoted ESIPT and AIE properties with large Stokes shifts and can be used as multiple-stimuli-responsive smart materials for many applications in mechanochromism, universal probes, chiral recognition, and living cell imaging.…”

Section: Introductionmentioning

confidence: 99%

Multiple Hydrogen Bonds Promoted ESIPT and AIE‐active Chiral Salicylaldehyde Hydrazide

et al. 2018

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The simpler, the better! A series of simple and highly fluorescent salicylaldehyde hydrazide molecules (41 samples) have been designed and prepared. Even though these soft materials contain a very small π‐conjugated system, they can go through multiple intramolecular and intermolecular hydrogen bonds promoted excited‐state intramolecular proton‐transfer (ESIPT) to display strong blue, green, yellow, and orange aggregation‐induced emission (AIE) with large Stokes shifts (up to 184 nm) and high fluorescence quantum yields (Ф up to 0.20). Unusual mechanochromic fluorescence enhancements are also found in some solid samples. Through coordination, hydrogen and halogen bonds, these flexible molecules can be used as Mg2+ (Ф up to 0.46) probes, universal anion (Ф up to 0.14) and unprotected amino acids (Ф up to 0.16) probes, and chiral diamine (enantiomeric selectivity and Ф up to 0.36 and 0.062, respectively) receptors. Combining their advantages of AIE and biocompatibility, these low cytotoxic dyes have potential application in living cell imaging. Furthermore, the effects of different functional groups on the molecule arrangement, ESIPT, AIE, probe, and chiral recognition properties are also examined, which provide a simple and bright paradigm for the design of multiple‐stimuli‐responsive smart materials.

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Mechanism of Fluorescence Switching in One ESIPT-Based Al³⁺ Probe

Cited by 36 publications

References 56 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

Solvent-Regulated Fluorimetric Differentiation of Al³⁺ and Zn²⁺ Using an AIE-Active Single Sensor

Multiple Hydrogen Bonds Promoted ESIPT and AIE‐active Chiral Salicylaldehyde Hydrazide

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Mechanism of Fluorescence Switching in One ESIPT-Based Al3+ Probe

Cited by 36 publications

References 56 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

Solvent-Regulated Fluorimetric Differentiation of Al3+ and Zn2+ Using an AIE-Active Single Sensor

Multiple Hydrogen Bonds Promoted ESIPT and AIE‐active Chiral Salicylaldehyde Hydrazide

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Mechanism of Fluorescence Switching in One ESIPT-Based Al³⁺ Probe

Solvent-Regulated Fluorimetric Differentiation of Al³⁺ and Zn²⁺ Using an AIE-Active Single Sensor