Excited-state Intramolecular Proton Transfer Fluorophore Research Articles

Water sensitive fluorescence tuning of V-shaped ESIPT fluorophores: Substituent effect and trace amount water sensing in DMSO

Highly sensitive nature of excited state intramolecular proton transfer (ESIPT) functionality in organic fluorophores made them potential candidates for developing environmental sensors and bioimaging applications. Herein, we report the synthesis of V-shaped Dapsone based Schiff base ESIPT derivatives (1–3) and water sensitive wide fluorescence tuning from blue to red in DMSO. Solid-state structural analysis confirmed the V-shaped molecular structure with intramolecular H-bonding and substituent dependent molecular packing in the crystal lattice. 1 showed strong solid-state fluorescence (λmax = 554 nm, Φf = 21.2 %) whereas methoxy substitution (2 and 3) produced tunable but significantly reduced fluorescence (λmax = 547 (2) and 615 nm (3), Φf = 2.1 (2) and 6.5 % (3)). Interestingly, aggregation induced emission (AIE) studies in DMSO-water mixture revealed water sensitive fluorescence tuning. The trace amount of water (less than 1 %) in DMSO converted the non-emissive 1–3 into highly emissive state due to keto tautomer formation. Further increasing water percentage produced deprotonated state of 1–3 in DMSO and enhanced the fluorescence intensity with red shifting of emission peak. At higher water fraction, 1–3 in DMSO produced aggregates and red shifted the emission with reduction of fluorescence intensity. The concentration dependent fluorescence study revealed the very low detection limit of water in DMSO. The limit of detection (LOD) of 1, 2 and 3 were 0.14, 1.04 and 0.65 % of water in DMSO. Hence, simple Schiff bases of 1–3 showed water concentration dependent keto isomer, deprotonated and aggregated state tunable fluorescence in DMSO. Further, scanning electron microscopic (SEM) studies of 1–3 showed water concentration controlled self-assembly and tunable fluorescence.

Experimental and theoretical comprehension of ESIPT fluorophores based on a 2-(2'-hydroxyphenyl)-3,3'-dimethylindole (HDMI) scaffold.

Excited-State Intramolecular Proton Transfer (ESIPT) emission is associated with intense single or multiple fluorescence in the solid-state, along with enhanced photostability and sensitivity to the close environment. As a result, ESIPT probes are attractive candidates for ratiometric sensing of a variety of substrates. A new family of ESIPT fluorophores is described herein, inspired by the well-known 2-(2'hydroxyphenyl)benzazole (HBX) organic scaffold. The connection of 3,3'-dimethylindole (or 3H-indole) derivatives with phenol rings triggers the formation of novel 2-(2'-hydroxyphenyl)-3,3'-dimethylindole (HDMI) fluorophores, capable of stimuli-responsive ESIPT emission. This brand new family of dyes displays redshifted emission, as compared to HBX, along with an unprecedented acid/base-mediated stabilization of different rotamers, owing to supramolecular interactions with methyl groups. These compounds are therefore highly sensitive to external stimuli, such as the presence of acid or base, where protonated and deprotonated species have specific optical signatures. Moreover, a new pyridine-functionalized HDMI dye displays acid-sensitive AIE properties. The photophysical properties of all compounds have also been studied using ab initio calculations to support experiments in deciphering the nature of the various radiative transitions observed and the related excited rotameric species.

Reproducible and High-Performance WOLEDs Based on Independent High-Efficiency Triplet Harvesting of Yellow Hot-Exciton ESIPT and Blue TADF Emitters.

Hot exciton organic light-emitting diode (OLED) emitters can balance the high performance of a device and reduce efficiency roll-off by fast reverse intersystem crossing from high-lying triplets (hRISC). In this study, an excited-state intramolecular proton transfer (ESIPT) fluorophore of 2-(benzo[d]thiazol-2-yl)-4-(pyren-1-yl)phenol (PyHBT) with the typical characteristic properties of a hot exciton is developed. With high efficiency of utilization of the exciton (91%), its yellow OLED exhibited high external quantum efficiency (EQE) of 5.6%, current efficiency (CE) of 16.8cdA-1 , and power efficiency (PE) of 17.3lmW-1 . The performance of the yellow emissive "hot exciton" ESIPT fluorophores is among the highest recorded. Due to the large Stokes shift of the ESIPT emitter, non-energy-transferred high-performance white OLEDs (WOLEDs) are developed, which are reproducible and highly efficient. This is possible because of the independent harvesting of most of the triplets in both complementary-color emitters without the interference of energy transfer. The PyHBT-based WOLEDs exhibit a maximum EQE of 14.3% and CE of 41.1cdA-1 , which facilitates the high-yield mass production of inexpensive WOLEDs.

A Selective Excited-State Intramolecular-Proton-Transfer (ESIPT) Sensor for Copper(II) Based on Chelation-Enhanced Quenching and "Off-On" Detection of Amino Acids.

We report the synthesis of 2-(4,5-diphenyl-1H-imidazole-2-yl)phenol (TPI-9) as an interesting fluorescent molecule displaying Excited-State Intramolecular-Proton-Transfer (ESIPT) with stokes shift of 120 nm. Phenolic compounds with the ability to form intramolecular hydrogen bonds and subsequent proton transfer are known as ESIPT fluorophores. Proton accepting ability can increase significantly by tailoring electron-donating groups. With the assistance of an environment-friendly organocatalyst, 10-camphor sulfonic acid (10-CSA), TPI-9 was synthesized to introduce substituents with electron-donating abilities to develop an efficient ESIPT mechanism. Factors influencing the emission, such as solvent, pH, and metal ions, are investigated. Quenching of fluorescence by Cu2+ through chelation enhancement quenching effect with a high selectivity allowed the establishment of a Cu2+ sensor with an LoD of 0.57 ppm and a ratiometric estimation with an LoD of 0.73 ppm. Metal binding (2 : 1) stoichiometry and quenching constant (0.0072 mol-1 s-1 ) are calculated from Job's and Stern-Volmer plots. Density functional theory (DFT) calculations are in accordance with the experimental results. Competitive replacement of TPI-9 by amino acids restores ESIPT, consequently, the fluorescence. Thus, an "off-on" fluorescence sensor for amino acid estimation is developed under 1 minute incubation. A linear relationship between amino acid concentration and fluorescence intensity is in 0-20 μg/mL range, and the LoD is less than 2.2 μg/mL.

Excited-State Polarizabilities: A Combined Density Functional Theory and Information-Theoretic Approach Study

Accurate and efficient determination of excited-state polarizabilities (α) is an open problem both experimentally and computationally. Following our previous work, (Phys. Chem. Chem. Phys. 2023, 25, 2131-2141), in which we employed simple ground-state (S0) density-related functions from the information-theoretic approach (ITA) to accurately and efficiently evaluate the macromolecular polarizabilities, in this work we aimed to predict the lowest excited-state (S1) polarizabilities. The philosophy is to use density-based functions to depict excited-state polarizabilities. As a proof-of-principle application, employing 2-(2'-hydroxyphenyl)benzimidazole (HBI), its substituents, and some other commonly used ESIPT (excited-state intramolecular proton transfer) fluorophores as model systems, we verified that either with S0 or S1 densities as an input, ITA quantities can be strongly correlated with the excited-state polarizabilities. When transition densities are considered, both S0 and S1 polarizabilities are in good relationships with some ITA quantities. The transferability of the linear regression model is further verified for a series of molecules with little or no similarity to those molecules in the training set. Furthermore, the excitation energies can be predicted based on multivariant linear regression equations of ITA quantities. This study also found that the nature of both the ground-state and excited-state polarizabilities of these species are due to the spatial delocalization of the electron density.

ESIPT-induced spin-orbit coupling enhancement leads to tautomer fluorescence quenching of the 10-HHBF molecule.

We present novel insights into the interplay between excited state intramolecular proton transfer (ESIPT) and spin-orbit coupling (SOC) in the 10-hydroxy-11H-benzo[b]fluoren-11-one (10-HHBF) molecule, utilizing the time-dependent density functional theory approach and femtosecond transient absorption spectroscopy. Our discoveries entail a reassessment of the luminescence mechanism for 10-HHBF, characterizing it as an ESIPT fluorophore. Additionally, we demonstrate that the molecule undergoes intersystem crossing (ISC) following proton transfer, which quenches the fluorescence of the proton-transferred state, thus resulting in the absence of dual emission and a limited spectral range of fluorescence. Furthermore, our investigation reveals that 10-HHBF displays an SOC enhancement feature induced by ESIPT, which facilitates the ISC process. This trait serves as a barrier to the application of 10-HHBF in single-molecule white light emitters (SMWLEs). Our findings underscore the notable influence of the ESIPT-induced spin-orbit interaction enhancement on luminescent properties, which necessitates consideration in the design of SMWLEs.

Influence of ethynyl extension on the dual-state emission properties of pyridinium-substituted ESIPT fluorophores

We describe the synthesis and photophysical properties in both solution and in the solid-state of dual-state emitters undergoing an Excited-State Intramolecular Proton Transfer (ESIPT) process. These fluorophores, built around the 2-(2′-hydroxyphenyl)benzoxazole (HBO) scaffold incorporate a N-methylpyridinium unit, at the 3 or 5 position of the phenol ring, prone to reduce the vibrational relaxation in the excited-state thanks to resonance effects and consequently allowing increasing the solution-state quantum yield (QY). In order to further optimize their optical properties, an additional ethynyl-extended triisopropylsilyl (TIPS) spacer was introduced with the aim to combine molecular rigidification and π-delocalization, as cooperative effects to enhance dual-state emission (DSE) properties. Molecular engineering studies and comparison with unsubstituted compounds reveal the significant impact of the position of the ethynyl-TIPS moiety on the photophysical properties, especially the fluorescence color. As several phenomena can compete with the ESIPT process, all dyes were modelled using ab initio calculations to rationalize the nature of the excited-states.

Third-order nonlinear optical manifestations in an intramolecular proton transfer fluorophore due to Tamm-plasmon based broadband optical absorbers

The imidazole ring has proven to be a very promising candidate for realizing molecular systems that facilitate efficient generation of broadband optical radiation using an excited-state intramolecular proton-transfer (ESIPT) mechanism. To obtain a targeted RGB-color composition, the conventional route is to create optimum mixtures of dyads and triads of non-interacting ESIPT molecules that cover the entire visible spectral band as well as restrict any energy transfer between wide bandgap donors and narrow bandgap acceptors. However, there is a need for alternate routes that can facilitate dynamic control over color composition during operation. The nonlinear optical (NLO) response of ESIPT fluorophores and configurations derived out of them could be explored from this perspective. In the present work, we design a T i O 2 / S i O 2 based distributed-Bragg-reflector (DBR) configuration with a terminating layer consisting of a film of an ESIPT fluorophore, namely, 2-(4,5-diphenyl-1-(4-(trifluoromethyl)phenyl)-1H-imidazol-2yl)phenol (DTIP). In the presence of thin Ag-film, the DTIP-DBR multilayer geometry supports a Tamm-plasmon-polariton (TPP) mode within the photonic bandgap of DBR, which exhibits an unusual spectral bandwidth greater than 50 nm. The open-aperture and closed-aperture Z-scan measurements reveal the strong TPP based broadband absorption that leads to reversal of third-order NLO characteristics, i.e., the multilayer geometry exhibits saturation absorption behavior at wavelengths where the bare DTIP fluorophore (in solution and film) shows a two-photon absorption signature.

Sterically Hindered 2‐(2’‐Hydroxyphenyl)benzoxazole (HBO) Emitters: Synthesis, Spectroscopic Studies, and Theoretical Calculations

AbstractWe describe various synthetic pathways to introduce sterically hindered substituents (mesityl, 2,4,6‐triisopropylphenyl, anthracene) to the proton donor side of excited‐state intramolecular proton transfer (ESIPT)‐capable 2‐(2’‐hydroxyphenyl) benzoxazole (HBO) fluorophores. Two original synthetic approaches were investigated in order to synthesize seven HBO derivatives. Optimization studies concluded that electron rich and bulky phosphine ligands are required to ensure completion of the Suzuki‐Miyaura cross‐coupling reaction involving a bulky aromatic boronic acid. The photophysical properties of all dyes revealed a strong influence of the nature of the solvent on the optical properties, as protic solvents tend to stabilize enol tautomers and induce dual emission. Our studies confirmed that, unlike the majority of organic dyes, ESIPT fluorophores do not undergo π‐stacking in the solid‐state. The nature of the excited‐states was explored by ab initio calculations.

Restriction of intramolecular torsion induces abnormal blue-shifted fluorescence in the aggregate state

The aggregation-induced emission (AIE) effect and corresponding restriction of intramolecular motions strategy are important mechanisms for regulating the performance of novel organic light-emitting diode materials and constituent molecules, such as emission intensity and peak position. Nevertheless, molecules in the aggregate state usually yield a red-shifted fluorescence due to the π-π interaction enhancement. Here, we report a blue-shifted fluorescence mechanism induced by the restriction of intramolecular torsion in the aggregate state for an interesting excited-state intramolecular proton transfer fluorophore. A combined experimental and theoretical method is performed to investigate the excited state dynamics of the molecules in solvent and the aggregate state respectively. Multiple regression analysis reveals that the changes of reorganization energy caused by AIE effect induce the blue-shifted fluorescence. These findings contribute in several ways to our understanding of the AIE effect, and provide a new strategy to regulate the emission performance of AIE materials.

Excited State Intramolecular Proton Transfer Based Fluorophores with Circularly Polarized Luminescence Emission

AbstractHerein, the first molecular design allowing the combination of circularly polarized luminescence (CPL) and excited state intramolecular proton transfer (ESIPT) fluorescence is described. In this novel class of emitters, the chiroptical activity originates from a chiral excitonic coupling induced by the tethering of two ESIPT fluorophores via a readily accessible trans‐1,2‐diaminocyclohexane scaffold. This approach has notably allowed the synthesis in a single step of a CPL‐active molecule displaying a very large Stokes shift (up to 12 087 cm−1 in toluene solution) and the synthesis in three steps of one of the rare examples of CPL‐active purely organic dual‐emission materials.

Photoinduced Generation of the π-Conjugated Zwitterionic State in the ESIPT Fluorophore of 2,4-Bisimidazolylphenol

We demonstrate that 2,4-bis(4,5-diphenyl-1H-imidazol-2-yl)phenol (2,4-bImP) undergoes photoinduced conversion into the so-called "π-conjugated zwitterion" after causing an excited-state intramolecular proton transfer (ESIPT) reaction. The powder sample of 2,4-bImP exhibits largely Stokes-shifted fluorescence characteristics to ESIPT fluorophores. On the other hand, its originally colorless solutions become colored when exposed to UV light for several minutes, whose color depends on the type of solvent. In particular, the CHCl3 solution rapidly turns dark green with the absorption maximum around 700 nm, and the colored solution is nearly restored to original by alternating addition of acid and base. To explain such drastic and reversible color changes, we hypothesized that the occurrence of ESIPT (i.e., deprotonation of the phenol and protonation of the imidazolyl group at its 2-position) triggered the charge-separated structure between the negatively charged phenolate and the positively charged imidazoliumyl group at its 4-position, which allowed resonance with the neutral p-quinoid structure. The formation of this π-conjugated zwitterion was strongly supported by the results of 1H and 15N NMR and Raman measurements.

Research Advances in Excited State Intramolecular Proton Transfer Fluorescent Probes Based on Combined Fluorescence Mechanism

Fluorescent probes can achieve rapid detection of analytes, and have become a research hotspot in recent years due to their excellent selectivity, high sensitivity and easy operation. Excited state intramolecular proton transfer (ESIPT) is one of the most basic strategies for designing fluorescence probes. Fluorescent probes based on ESIPT possess large Stokes shift, strong luminescence and high fluorescence quantum yield. However, these are still some disadvantages, such as sensitivity to the environment and short emission wavelength. In recent years, the ESIPT combined with other fluorescence mechanisms, can obtain new fluorescent probes with dual mechanism of fluorescence response. This strategy can not only solve the shortage of ESIPT fluorophore, but also realize multi-fluorescence signal channel, and significantly improve the selectivity and sensitivity of the new probe. In this review, we mainly summarized the detection mechanism and imaging application of fluorescence probes of PET-ESIPT, ICT-ESIPT, FRET-ESIPT, AIE-ESIPT for ions, small molecules, biological macromolecules in recent years.

ESIPT fluorophores derived from 2,3-dichloro-5,6-dicyano-p-benzoquinone based carbon dots for dual emission and multiple anti-counterfeiting.

Fluorophores and hydrogen bonding interactions play key roles in the fluorescence properties of bottom-up carbon dots. In this work, an excited-state intramolecular proton-transfer (ESIPT) active fluorophore, 5-chloro-6-ethoxy-4,7-dihydroxyisoindoline-1,3-dione (CEDD) and a non-ESIPT 7-cyano-5,8-dihydroxyquinoxaline-6-carboxamide (CDQC) are extracted from 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) based carbon dots. The enol form of CEDD shows a weak blue, small Stokes shift and short lifetime emission under the aprotic or alkali conditions, but the keto form exhibits a strong green, large Stokes shift and long lifetime emission in a protic or an acidic environment. Due to the lack of the ESIPT process, CDQC has no dual emission characteristics, but shows efficient solid-state emission. By virtue of the ESIPT ability of CEDD, multiple anti-counterfeiting methods are achieved by using hydrogen chloride, ammonia, and fluorescence lifetime imaging, as well as dimethyl sulfoxide as the encryption/decryption tools.

Easily Accessible Schiff Base ESIPT Molecules with Tunable Solid State Fluorescence: Mechanofluorochromism and Highly Selective Co2+ Fluorescence Sensing

AbstractSchiff base molecules of 1–4 ((E)‐N′‐benzylidene‐2‐hydroxybenzohydrazide derivatives) showed structure controlled solid state fluorescence tuning, reversible stimuli induced fluorescence switching and highly selective Co2+ sensing. The strong intramolecular H‐bonding between imine and amine facilitates excited state intramolecular proton transfer (ESIPT) and large red shifted solid state fluorescence. Positional isomers and substitutional change tuned the solid state fluorescence (460 to 605 nm). The substituents and positions control stimuli‐induced fluorescence switching. ESIPT fluorophores showed strong fluorescence in DMF (Φf=0.057 to 0.35 compared to quinine sulphate). ESIPT fluorophores (2–4) exhibited highly selective fluorescence sensing of Co2+ ions without significant interference from other metal ions. Concentration dependent studies of fluorophores show the detection limit (LOD) of 54 nM that is much lower than the Environmental Protection Agency (EPA) guideline value (1.7 μM) in drinking water. Solid state fluorescence of ESIPT fluorophores have been made use to fabricate solid fluorescence assay (PVA polymer composite thin films) and demonstrated highly selective fluorescence sensing of Co2+ upon dipping into aqueous metal ions solution. Thus, the present studies demonstrate the versatility of Schiff base molecules for developing ESIPT fluorophores for stimuli responsive materials and highly selective fluorescence sensing both in solution and solid state.

Polarity-Induced Excited-State Intramolecular Proton Transfer (ESIPT) in a Pair of Supramolecular Isomeric Multifunctional Dynamic Metal-Organic Frameworks.

A pair of supramolecular isomers of CdII -based MOF have been synthesized by utilizing a flexible N,N'-donor linker and a dicarboxylate with ESIPT (excited-state intramolecular proton transfer) fluorophore by varying the reaction media. One of the MOFs has a 3D four-fold interpenetrating framework with guest solvent in the structure that undergoes a solvent-dependent crystalline-to-crystalline structural transformation, which has been extensively studied by powder XRD and IR spectroscopy. The other MOF is structurally rigid in nature and has a two-fold interpenetrating structure without any guest molecules. Both the compounds show moderate CO2 adsorption and one of them, the MOF with the four-fold interpenetrating structure, also shows moderately high H2 adsorption. Furthermore, both the compounds show interesting luminescence behavior. In the solid state, the two compounds show single-peak spectra, whereas upon suspension of these compounds in polar solvents, the maxima split into two peaks with a large Stokes shift. On the other hand, in nonpolar solvents, only one emission maximum is observed. This solvatochromic dual-emission phenomenon is due to ESIPT, which has been extensively studied.

Demonstration of Baird's rule complementarity in the singlet state with implications for excited-state intramolecular proton transfer.

The aromatic character of an arene is proposed to switch from aromatic in the ground state (S0) to antiaromatic in the S1 and T1 excited states. This behavior is known as Baird's rule and has been invoked to explain excited-state properties, primarily in the triplet state, whereas rationalization of antiaromaticity in the singlet state is less developed. This work demonstrates the first application of Baird's rule to rationalize previously unexplained experimental behavior of the singlet state process known as excited-state intramolecular proton transfer (ESIPT). Further, by analyzing the variations in isotropic magnetic shielding around the base arenes (benzene and naphthalene) of ESIPT fluorophores in the S0 and S1 electronic states, different shielding distributions indicate a complementarity to Baird's rule: greater aromaticity in S0 leads to greater antiaromaticity in S1 and vice versa. These findings have immediate application in the design of functional ESIPT fluorophores and, more generally, for photochemical reactions that are driven by the relief of antiaromaticity in the excited state. Notably, a tenet of traditional chromophore design states that expansion of conjugation generally leads to a red-shift in absorbance and emission wavelengths. The results of this study show that ESIPT fluorophores run contrary to those conventional design principles and this behavior can only be rationalized by considering Baird's rule.

Highly sensitive fluorescent probe based on a novel phenothiazine dye for detection of thiophenols in real water samples and living cells.

Based on an excited-state intramolecular proton transfer (ESIPT) fluorophore, a novel fluorescent off-on probe for detection of thiophenols was designed and synthesized. This probe (λex = 401nm, λem = 527nm) displayed high specificity for sensing thiophenols over other biologically related species. Besides, this probe possessed capabilities of monitoring thiophenols with rapid response rate (3min), a large Stokes shift (126nm), and high sensitivity (2.7nM). The sensing mechanism was considered to be that thiophenols triggered thiolysis of the probe and the ESIPT fluorophore was released, as confirmed by means of HPLC and HRMS. Most notably, this probe was successfully applied to monitor levels of thiophenols in realistic samples and MDA-MB-231 cells. Graphical abstract A novel phenothiazine-based fluorescent probe was developed for sensitively sensing thiophenols in both aqueous medium and living cells.

Color Changes of a Full-Color Emissive ESIPT Fluorophore in Response to Recognition of Certain Acids and Their Conjugate Base Anions.

2-(1,3-Benzothiazol-2-yl)-4-methoxy-6-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol (BTImP) is an excited-state intramolecular proton transfer (ESIPT) fluorophore, containing an acid-stimuli-responsive intramolecular hydrogen bond (H-bond) that can switch from the central phenolic proton to the imidazole (Im) or benzothiazole (BT) nitrogen atoms. Here, we demonstrate that BTImP shows full-color (red, green, blue, and white) emission upon the addition of different concentrations of HClO4 or, with time, after the addition of HBF4 . It also shows thermally dependent color changes from pink through white to blue in a narrow temperature range of 25-60 °C. 1 H and 15 N NMR measurements suggest that, after the green fluorescent BTImP is protonated at its Im nitrogen atom, a conjugate base anion coordinates to the imidazolium (HIm+ ) proton, forming two types of complexes with different coordination states. One state shows a significantly Stokes-shifted red emission resulting from ESIPT at the BT side, whereas the other shows a typical Stokes-shifted blue emission, probably caused by interaction of the anion with the phenolic proton, which breaks the H-bond on the BT side. BF4- and ClO4- are effective in forming such a blue emitter, whereas Cl- and PF6- are not; this behavior depends on whether the anion can fit into the bidentate binding site consisting of HIm+ and the phenolic hydroxy group.

An ESIPT Fluorophore Based on Zinc‐Induced Intramolecular Proton Transfer between Ligands in the Complex

The zinc complex ZnE containing two 2‐(2′‐hydroxyphenyl)‐1‐ethyl‐4‐hydroxybenzimidazole (EtL) ligands has been designed and synthesized. The zinc ion acts as a spacer linking the two coordinated EtL, between which intramolecular hydrogen bonds form. Upon excitation, in addition to a weak emission at 399 nm, ZnE exhibits strong excited‐state intramolecular proton‐transfer (ESIPT) emission with a maximum at 479 nm with a large Stokes shift (8449 cm–1) in tetrahydrofuran solution. Importantly, the ESIPT in ZnE also takes place in the powder form, resulting in dual emission (407 and 490 nm) with total photoluminescence quantum yields (Φ) of 0.16. The results of quantum calculations suggest that the ESIPT fluorescence is based on a zwitterionic excited‐state species resulting from a single proton transfer between the ligands.