Excited-state Intramolecular Proton Transfer Research Articles

ESIPT-induced intersystem crossing leads to tautomer fluorescence quenching for 3-mercapto-2-(4-(trifluoromethyl)phenyl)-4H-chromen-4-one molecule

The excited-state intramolecular proton-transfer (ESIPT) dynamics of 2-(4-(diethylamino)phenyl)-3-mercapto-4H-chromen-4-one (3NTF) and 3-mercapto-2-(4-(trifluoromethyl)phenyl)-4H-chromen-4-one (3FTF) have been investigated using time-dependent density functional theory (TDDFT). Upon photoexcitation, 3NTF exhibits a single fluorescence emission while 3FTF is fluorescence quenched when dissolved in cyclohexane solution. The present study reveals that both species undergo barrierless ESIPT process, and the underlying reason for fluorescence quenching in 3FTF has been elucidated. Specifically, it is concluded that intersystem crossing (ISC) is responsible for the fluorescence quenching in the 3FTF molecule due to the energy gap between the S1 and T2 states is only 0.12 eV plus large S1 → T2 spin–orbit coupling resulting in a strong interaction between the singlet and triplet states. The present study provides a reference for the fluorescence quenching associated with thiol-hydrogen bond molecules, and it is helpful for further research on ESIPT reactions of sulfur-containing molecules.

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Excited‐state intramolecular proton transfer (ESIPT) enables the rearrangement of photoinduced charge distribution and results in the structural isomerization in the excited state. The EISPT mechanism can be used for optimizing the photocatalytic performances of β‐ketoenamine‐linked two‐dimensional covalent organic frameworks (COFs). It has been demonstrated that the modification of building blocks with electron‐withdrawing cyano‐groups benefits the ESIPT‐induced photoisomerization for COFs, thereby promoting photocatalytic activity and achieving the excellent hydrogen evolution performances from water splitting. More details are discussed in the article by Guo et al. on pages 2621—2626.image

Excited-state intramolecular proton transfer (ESIPT) salicylaldehyde Schiff bases: ratiometric sensing of ammonia and biologically relevant ions in solution and solid state

ABSTRACT The intricate molecular architecture of ESIPT salicylaldehyde Schiff bases facilitates dynamic processes, inducing tunable photoluminescent properties. Notably, their halochromic nature, exhibiting colour changes in response to external stimuli, adds a vibrant dimension to their molecular repertoire. This sensitivity extends to environmental factors, making them valuable indicators for alterations in surroundings. The compound (E)-N’-(3,5-dibromo-2-hydroxybenzylidene)-4-methylbenzohydrazide (PTBH) demonstrates exceptional sensitivity to ammonia, enabling real-time detection (LOD = 0.14 nM) in both solution (ratiometric) and the solid state. Moreover, their metal chelation capability allows simultaneous sensing of Mg2+ and Fe2+ ions, addressing environmental hazards. Exploiting molecular recognition, the fluorescent probe serves as sensors for amino acids, opening new avenues in biomedical diagnostics. The study introduces a novel solid-state emissive Schiff base, highlighting its stimuli-responsive photoluminescent properties and diverse applications, emphasising its potential in intelligent fluorescent materials for analytical and sensing technologies.

Flexible organic crystals with multi-stimuli-responsive CPL for broadband multicolor optical waveguides.

Flexible organic crystals, capable of transmitting light and responding to various external stimuli, are emerging as a new frontier in optoelectronic materials. They hold immense potential for applications in molecular machines, sensors, displays, and intelligent devices. Here, we report on flexible organic crystals based on single-component enantiomeric organic compounds, demonstrating multi-stimuli-responsive circularly polarized light (CPL). These crystals exhibit remarkable elasticity, responsiveness to light and acid vapors, and tunable circularly polarized optical signals. Upon exposure to acid vapors, the fluorescence of the crystals shifts from initial yellow emission to green emission, attributable to the protonation-induced inhibition of excited-state intramolecular proton transfer. Under UV irradiation, the fluorescence emission undergoes a red-shift, resulting from the molecular transformation from an enol configuration to a ketone configuration. Notably, both processes are reversible and can be restored under daylight. The integration of reversible fluorescence changes under light and acid vapors stimuli, CPL signals, and flexible optical waveguides within a single crystal paves the way for the application of organic crystals as all-organic chiral functional materials.

Theoretical Investigation on Proton Transfer Directionality and Dynamics Behavior of 3-(Benzo[d]thiazol-2-yl)-2-hydroxy-5-methoxybenzaldehyde with Two Asymmetric Proton Acceptors.

A detailed theoretical investigation on the excited state intramolecular proton transfer (ESIPT) directionality and dynamics behavior of 3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methoxybenzaldehyde (BTHMB) with two unsymmetric proton acceptors (N and O2) has been performed. The hydrogen bond O1-H···N in BTHMB-a formed by the O1-H group with the N atom or O1-H···O2 in BTHMB-b formed by the O1-H group with the O2 atom is enhanced upon photoexcitation, and the strength of the O1-H···N bond is stronger, which will drive the O1-H proton to the N atom. Potential energy curves further confirm that ESIPT occurs in the N atom because of the smaller energy barrier (0.39 kcal/mol). Results of dynamics simulations manifest that no surface hopping exists between the S0 and S1 states within 300 fs, and ESIPT time constants of BTHMB-a and BTHMB-b are 48 and 151 fs, respectively. While the reverse ESIPT is observed in BTHMB-b at 294 fs, implying that the O1-H proton is transferred to the N atom instead of the O2 atom. The consistency of the calculated absorption (390 nm) and fluorescence spectra (443 and 602 nm) of BTHMB-a with the experimental values (390, 410, and 605 nm) confirms this conclusion again. The charge distribution analysis shows that the charge on the proton acceptors increases, and the O2 atom has higher electronegativity because it has more negative charges. The minimum surface electrostatic potential on the N atom in BTHMB-b correlating with the pKb value is -47.38 kcal/mol, indicating that the N atom has strong basicity. Therefore, the basicity of the N atom dominates the ESIPT process rather than the electronegativity of the O2 atom.

A dual-response fluorescent hemicyanine probe for the detection of mitochondrial hypochlorite and viscosity based on ESIPT/AIE and TICT

Viscosity and hypochlorite (ClO−) are two important factors affecting the physiological activity and function of mitochondria. Hypochlorite (ClO−) is a vital reactive oxygen species, and endogenous ClO− acts as an important germicidal oxidant in the immune system at low concentrations. While, fluctuations in viscosity can cause mitochondrial dysfunction that is linked to several diseases. We herein report on a hemicyanine-based probe (BDTB-PA) for the detection of hypochlorite (ClO−) and viscosity. The probe exhibits a very low fluorescence background in an aqueous solution due to twisted intramolecular charge transfer (TICT) and blocked excited-state intramolecular proton transfer (ESIPT). In a viscous solution, the TICT of the probe was inhibited, generating a strong emission at 580 nm. In contrast, upon treatment with ClO−, the phenylboronic acid pinacol ester group of probe BDTB-PA was removed, and the hydroxyl group was released, activating the ESIPT process. Coupled with its aggregation-induced emission (AIE) characteristics, the product of BDTB-PA with ClO− exhibited a distinct emission at 540 nm. As such a solution of the probe BDTB-PA exhibited a distinct fluorescent color change from colourless to green under UV light with the addition of ClO−. More importantly, probe BDTB-PA was used for monitoring ClO− and viscosity in the mitochondria of living cells, plants and zebrafish.

Visible‐Light‐Driven Solid‐State Fluorescent Photoswitches for High‐Level Information Encryption

Developing visible‐light‐driven fluorescent photoswitches in solid state remains an enormous challenge in smart materials. Such photoswitches are obtained from salicylaldimines through excited‐state intramolecular proton transfer (ESIPT) and subsequent cis‐trans isomerization strategies. By incorporating a bulky naphthalimide fluorophore into Schiff base, three photoswitches achieve dual‐mode changes (both color and fluorescence) in the solid state. In particular, the optimal one generates triple fluorescence changing from green, to yellow and finally orange upon visible light irradiation. This switching process is fully reversible and can be repeated at least 10 times without obvious attenuation, suggesting its superior photo‐fatigue resistance. Mechanism studies reveal that naphthalimide group not only enables the tuning of multicolor with an additional emission, but also induces a folded structure, reducing molecular stacking and facilitating ESIPT and cis‐trans isomerization. As such, photopatterning, ternary encoding and transient information recording and erasing are successfully developed. The present study provides a reliable strategy for visible‐light‐driven fluorescent photoswitches, showing implications for advanced information encryption materials.

Tunable Emission and Structural Insights of 6-Arylvinyl-2,4-bis(2'-hydroxyphenyl)pyrimidines and Their O∧N∧O-Chelated Boron Complexes.

In this study, we present the synthesis and photophysical characteristics of a novel series of 6-arylvinyl-2,4-bis(2'-hydroxyphenyl)pyrimidines. These compounds exhibit nonemissive properties attributed to the potential occurrence of a excited-state intramolecular proton transfer process from the OH groups to the nitrogen atoms of the pyrimidine ring. The introduction of an acid for protonation of the pyrimidine ring results in a significant enhancement of the fluorescence response, easily perceptible to the naked eye. Notably, these molecules serve as intriguing rigid O∧N∧O ligands for boron chelation. The incorporation of boron atoms promotes structural planarity, increases rigidity, and successfully restores fluorescence in both solution and the solid state. Moreover, the photoluminescence was found to be strongly influenced by the nature of the end groups on the arylvinylene fragment, allowing for the modulation of the emission color and covering the optical spectrum from blue to red. Strong emission solvatochromism was observed in various solvents, a finding that supports the formation of intramolecular charge-separated emitting states, particularly when terminal electron-donating groups are present in the structure. X-ray diffraction analysis enables the determination of inter- and intramolecular interactions, as well as molecular packing structures, aiding in the rationalization of distinct luminescent behaviors in the solid state. All experimental findings are elucidated through extensive density functional theory (DFT) and time-dependent DFT calculations.

Incorporation of ESIPT into pillar[5]arene for solid-state dual emission responsive to n-hexane vapor

Abstract Pillar[5]arene is a promising macrocyclic receptor of a chemical sensor showing shape-selective encapsulation of neutral molecules into the cavity, but the poor fluorescence properties remain a challenge. Herein, we report a pillar[5]arene coupled with 2-(2-hydroxyphenyl)benzoxazole (HBO), which displays bright fluorescence in both solution and the solid state. Owing to the excited-state intramolecular proton transfer (ESIPT) in the HBO moiety, greatly improved fluorescence is observed for the pillar[5]arene derivative in CHCl3 (Φlum = 11%) and powder form (Φlum = 25%). Moreover, the emission color changes from light green to blue when the powder sample is exposed to n-hexane vapor. The color change derives from variable dual emission via ESIPT and excimer-forming pathways, as suggested by fluorescence lifetime measurements at different wavelengths. Powder x-ray diffraction indicates that increased crystallinity and a small alteration in the solid-state structure leads to visible fluorescent chromism upon vapor encapsulation.

A ‘Turn-on’ fluorogenic probe for selective and specific detection of Hg(II) ions

Mercury (Hg2+) and its associated compounds have drawn serious concern from the scientific communities for their extreme toxicity to human beings. The present article introduced a chromone-benzoxazole embracing an effective fluorogenic probe, (E)-3-(((4-(benzo[d]oxazol-2-yl) phenyl) imino) methyl)-2-methoxy-2H-chromen-4-ol (BPMC) for selective and specific detection of Hg2+ ions having detection and quantification limit in the µM range. A significant photoluminescence enhancement has been observed from BPMC solution (water-DMSO mixture, 50 % v/v) displaying low to highly intense blue-violet photoluminescence under a 365 nm UV lamp due to the inhibition of intramolecular charge transfer (ICT) and excited state intramolecular proton transfer (ESIPT) processes involved in BPMC. Furthermore, to achieve on-site detection of Hg2+ ions and investigate the practical utility of our developed probe, we have fabricated a BPMC-stained paper-strips-based test kit and demonstrated its practical effectiveness for on-spot detection. The details of the detection mechanism have been revealed through 1H NMR, FT-IR, and high-resolution mass spectrometric analysis. The present report evokes a broader perspective for tailoring ICT and ESIPT-based chromo-fluorogenic probes to accelerate their real-world application and environmental monitoring.

Color-tunable and white circularly polarized luminescence through confining guests into chiral MOFs.

Herein, chiral metal-organic frameworks (MOFs), DCF-20 and LCF-20, were utilized as matrices for both chirality transfer and energy transfer. HBT1@MOFs and HBT2@MOFs emit excitation-dependent circularly polarized luminescence (CPL) due to excited-state intramolecular proton transfer (ESIPT). HBT1/C152/NIR@MOFs exhibit full-color and white CPL. The luminescence dissymmetry factors (glum) were significantly increased, benefiting from the efficient chirality space transfer and high luminescence efficiency.

Theoretical study on precise regulation of ESIPT reaction based on ICT effect of o-carborane derivatives

The unique stereocarborane fluorophore design has attracted widespread attention because of its ability to effectively enhance the performance of thin-film fluorescence sensors. This study provides a detailed theoretical investigation of the excited-state intramolecular proton transfer (ESIPT) reactions of three o-carborane derivatives, NaCBO, PaCBO and PyCBO, using density functional theory and time-dependent density functional theory. We found that as the number of benzene rings in the electron donor groups increases, the interaction between the first excited-state electron donor–acceptor fragments is enhanced, weakening the intramolecular hydrogen bonding strength, which in turn inhibits the ESIPT. Notice that the intramolecular charge transfer (ICT) is proportional to the interaction between electron donor and acceptor fragments with the analysis of electron structure. The higher the ICT level of the target system, the more unstable the keto form generated by ESIPT. Therefore, the ESIPT can be precisely manipulated by rationally adjusting the ICT effect. Furthermore, with increasing solvent polarity, the photophysical properties of the chromophores exhibit non-solvatochromism. This is attributed to the rigid o-carborane structure, which serves as a spatial scaffold to increase the adaptability of the molecule to the environment. This study is expected to provide theoretical guidance and new ideas for preparing high-performance thin-film fluorescence sensing.

Constructing ESIPT-Capable α-Cyanostilbene Luminogens: Influence of Different Aromatic Substitutions Tethered to H-Acceptor (CH = N) on Photophysical Properties, Cu2+ and Fe3+ Detection.

Herein, two excited-state intramolecular proton transfer (ESIPT)-capable α-cyanostilbene luminogens were synthesized by Schiff base reaction of salicylaldehyde-like α-cyanostilbene candidate with 1-naphthylamine and 3-biphenylamine, respectively. We systematically analyzed their photophysical properties compared with their analogue, and demonstrated that their fluorescence behaviors could be elaborately modulated by different aromatic substitutions tethered to H-acceptor (CH = N). In virtue of the outstanding solid fluorescence, the 3-biphenylamine-decorated fluorophore was applied for monitoring Cu2+/Fe3+ qualitatively on the TLC-based test strip in real time and sensing Cu2+/Fe3+ quantitatively in the THF/H2O medium (fw = 90%, pH = 7.4). When the probe chelated with Cu2+/Fe3+, similar "turn-off" fluorescence signal outputs were triggered. From the fluorescence titration experiments, the detection limits were evaluated as 7.97 × 10- 8 M for Cu2+ and 8.24 × 10- 8 M for Fe3+, and the binding constant (Kα) values of the complexes were found to be 7.80 × 104 M-1 for Cu2+ and 9.06 × 104 M-1 for Fe3+. Job's plots indicated that probe complexed with Cu2+/Fe3+ in a 2:1 binding stoichiometry ratio. Furthermore, the probe was used to accurately quantify the Fe3+ spiked in real water specimens. This study offered a new perspective to construct ESIPT-capable α-cyanostilbene luminogen as the potential luminescent probe.

Multiple Enol-Keto Isomerization and Excited-State Unidirectional Intramolecular Proton Transfer Generate Intense, Narrowband Red OLEDs.

A novel series of excited-state intramolecular proton transfer (ESIPT) emitters, namely, DPNA, DPNA-F, and DPNA-tBu, endowed with dual intramolecular hydrogen bonds, were designed and synthesized. In the condensed phase, DPNAs exhibit unmatched absorption and emission spectral features, where the minor 0-0 absorption peak becomes a major one in the emission. Detailed spectroscopic and dynamic approaches conclude fast ground-state equilibrium among enol-enol (EE), enol-keto (EK), and keto-keto (KK) isomers. The equilibrium ratio can be fine-tuned by varying the substitutions in DPNAs. Independent of isomers and excitation wavelength, ultrafast ESIPT takes place for all DPNAs, giving solely KK tautomer emission maximized at >650 nm. The spectral temporal evolution of ESIPT was resolved by a state-of-the-art technique, namely, the transient grating photoluminescence (TGPL), where the rate of EK* → KK* is measured to be (157 fs)-1 for DPNA-tBu, while a stepwise process is resolved for EE* → EK* → KK*, with a rate of EE* → EK* of (72 fs)-1. For all DPNAs, the KK tautomer emission shows a narrowband emission with high photoluminescence quantum yields (PLQY, ∼62% for DPNA in toluene) in the red, offering advantages to fabricate deep-red organic light-emitting diodes (OLED). The resulting OLEDs give high external quantum efficiency with a spectral full width at half-maximum (FWHM) as narrow as ∼40 nm centered at 666-670 nm for DPNAs, fully satisfying the BT. 2020 standard. The unique ESIPT properties and highly intense tautomer emission with a small fwhm thus establish a benchmark for reaching red narrowband organic electroluminescence.

AI-Powered Mining of Highly Customized and Superior ESIPT-Based Fluorescent Probes.

Excited-state intramolecular proton transfer (ESIPT) has attracted great attention in fluorescent sensors and luminescent materials due to its unique photobiological and photochemical features. However, the current structures are far from meeting the specific demands for ESIPT molecules in different scenarios; the try-and-error development method is labor-intensive and costly. Therefore, it is imperative to devise novel approaches for the exploration of promising ESIPT fluorophores. This research proposes an artificial intelligence approach aiming at exploring ESIPT molecules efficiently. The first high-quality ESIPT dataset and a multi-level prediction system are constructed that realized accurate identification of ESIPT molecules from a large number of compounds under a stepwise distinguishing from conventional molecules to fluorescent molecules and then to ESIPT molecules. Furthermore, key structural features that contributed to ESIPT are revealed by using the SHapley Additive exPlanations (SHAP) method. Then three strategies are proposed to ensure the ESIPT process while keeping good safety, pharmacokinetic properties, and novel structures. With these strategies, >700 previously unreported ESIPT molecules are screened from a large pool of 570000 compounds. The ESIPT process and biosafety of optimal molecules are successfully validated by quantitative calculation and experiment. This novel approach is expected to bring a new paradigm for exploring ideal ESIPT molecules.

An insight into the role of ESIPT/TICT-based antioxidant flavone analogues in fluoro-probing diabetes-induced viscosity changes: a unified experimental and theoretical endeavour.

Potent antioxidants, like 3-hydroxy flavones, attracted considerable attention due to their excited state intramolecular proton transfer (ESIPT)-based fluorescence behaviour. This article is an interesting demonstration of a series of synthetic 3-hydroxy flavone analogues having high antioxidant activity as molecular rotor-like viscosity probes. Among these flavone analogues, 4'-N,N-dimethylamino-3-hydroxy flavone (3) is the most potent one, showing the twisted intramolecular charge transfer (TICT)-dependent fluoroprobing activity toward the blood viscosity changes associated with diabetes and free fatty acids (FFA)-induced nuclear viscosity changes of MIN6 cells. The TICT dynamics of (3), which instigates its viscosity probing activity, was comprehended with the help of DFT-based computational studies. Abnormal cellular viscosity changes are the pathological traits for various diseases, and non-toxic flavone-based viscosity probes can be useful for diagnosing such pathological conditions.

Photophysical properties of 2’-hydroxychalcones of 2-cinnamoyl-4-nitro-1-naphthol series

2’-Hydroxychalcones of 2-cinnamoyl-4-nitro-1-naphthol series were obtained by the condensation between 2-acetyl- 4-nitro-1-naphthol and benzaldehydes. The presence of the 4-positioned nitro group in the 1-hydroxy-2-naphthyl fragment contributes to the excited state intramolecular proton transfer (ESIPT) fluorescence of these 2’-hydroxy- chalcones in the solid state. Compound with dimethyl- amino substituent, 2-(4-dimethylaminocinnamoyl)-4-nitro- 1-naphthol, also demonstrates ESIPT in solution.

Deciphering TADF Mechanisms in Metal-Free Organic Emitters BrA-HBI: Utilizing Optimally Tuned Range-Separated Functionals for Insight

Abstract Metal-free organic emitters, characterized by their thermally activated delayed fluorescence (TADF) properties, offer considerable promise for the creation of highly efficient organic light-emitting diodes (OLEDs). Recently, Shao et al. presented a novel excited state intramolecular proton transfer (ESIPT) system BrA-HBI, demonstrating an emission quantum yield of up to 50% [Adv. Funct. Mater. 32, 2201256 (2022)]. However, many open issues cannot be answered solely by experimental means only and require detailed theoretical investigations. For instance, what causes the activation of TADF from the Keto* tautomer and leads to fluorescence quenching in the Enol* form? Herein, we provide a theoretical investigation on the TADF mechanism of the BrA-HBI molecule by optimally tuned range-separated functionals. Our findings reveal that ESIPT occurs in the BrA-HBI molecule. Moreover, we have disclosed the reason for the fluorescence quenching of the Enol* form and determined that the T 2 state plays a dominant role in the TADF phenomenon. In addition, double hybrid density functionals method was utilized to verify the reliability of optimally tuned range separation functionals on the calculation of the TADF mechanism in BrA-HBI. These findings not only provide a theoretical reference for development of highly efficient organic light-emitting diodes, but also demonstrate the effectiveness of the optimally tuned range-separated functionals in predicting the luminescence properties of TADF molecules.

Emissively enhanced novel azo compounds featuring with ESIPT core

This study presents the synthesis and detailed characterization of novel azo compounds featuring Excited State Intramolecular Proton Transfer (ESIPT) cores derived from orcinol, resorcinol, and 2-naphthol. Using a comprehensive suite of spectroscopic techniques, including Nuclear Magnetic Resonance (NMR), Liquid Chromatography-Mass Spectrometry (LC-MS), Ultraviolet-Visible (UV–Vis) spectroscopy, and fluorescence spectroscopy, we explored the unique photophysical properties of these compounds. Notably, the synthesized compounds exhibited exceptionally large Stokes shifts, with values recorded at 204 nm, 251 nm, and 168 nm for compounds 1A, 2A, and 3A, respectively. These shifts indicate significant potential for applications in areas such as optical sensing and fluorescent imaging. Furthermore, Density Functional Theory (DFT) calculations were employed to investigate the nonlinear optical (NLO) properties of the enol and keto tautomeric forms of these compounds. The findings revealed that compound 2A, in particular, demonstrated impressive first-order hyperpolarizability, especially in chloroform, underscoring its suitability for advanced nonlinear optical applications. The study highlights the pivotal role of the ESIPT mechanism, where efficient intramolecular hydrogen bonding facilitates proton transfer upon excitation, leading to enhanced fluorescence properties. This phenomenon is particularly pronounced in compound 2A, where dual O—H interactions contribute to its remarkable fluorescence behavior, making it a standout candidate for use in high-performance optical materials. These findings not only advance our understanding of azo compounds and their versatile photophysical characteristics but also open new avenues for their application in cutting-edge technologies such as optical sensors, imaging agents, laser materials, and other fluorescence-based devices. By strategically leveraging the ESIPT process and the unique structural features of these compounds, this research paves the way for future innovations in the field of advanced optical materials and photonic devices.

Uncovering excited state behaviours associated with electron-withdrawing CN and electron-donating TPA moieties on SAA derivatives: a theoretical study

Inspired by the excellent photochemical characteristics exhibited by salicylaldehyde azine (SAA) derivatives, our current endeavour primarily revolves around delving into the intricacies of photo-induced excited state reactions for its electron-donating and electron-withdrawing moieties derivatives (i.e. CN-SAA-CN, CN-SAA-TPA and TPA-SAA-TPA). Our simulations reveal push–pull-substituted-dependent photoexcitation that could significantly affect excited state intramolecular proton transfer (ESIPT) reaction for SAA derivatives. Constructing potential energy surfaces (PESs), we unveil the ultrafast ESIPT mechanism due to the low potential barriers. Additionally, by comparing the differences of barriers among CN-SAA-CN, CN-SAA-TPA and TPA-SAA-TPA, we present regulative manner for SAA derivatives by substituting electron-donating and electron-withdrawing moieties. We sincerely anticipate that the modulation of push–pull substitutions on excited state behaviours will pave the way for ground-breaking advancements in luminescent materials.