Excited-state Intramolecular Proton Transfer Process Research Articles

One-step synthesis of a sparkling fluorescent chemodosimeter: Selective and sensitive detection of triphosgene and application in tracing triphosgene in soil

We have developed a glowing fluorescent chemodosimeter that utilizes excited-state intramolecular proton transfer (ESIPT) through a one-step synthesis process. This innovative chemodosimeter exhibited remarkable selectivity and sensitivity in detecting triphosgene, achieving a limit of detection (LOD) of 41 nM. The strong fluorescence of this probe at 504 nm was significantly quenched by triphosgene. This phenomenon is attributed to the formation of a new adduct upon the addition of guest, which restricts the ESIPT process and ultimately completely extinguishes the fluorescence. Furthermore, we have successfully extended the utility of this probe to determine trace amounts of triphosgene in soil samples of varying composition in solution and strip-based experiments. Notably, our chemodosimeter demonstrates effectiveness across a spectrum of soil types, detecting micromolar levels of triphosgene in complex soil matrices with a LOD of 1.59 µM. the promising sensing of triphosgene in complex soil system hold potential detection of extremely toxic chemical warfare presence in the environment.

Rapid sequential detection of Al3+ and glyphosate using an “Off-On-Off” fluorescent probe based on salicylate modified layered double hydroxides

A fluorescent probe based on salicylate modified layered double hydroxide (LDH-SA) is presented, enabling the swift sequential detection of Al3+, fosetyl-Al and glyphosate in aqueous environment. The probe was synthesized using a simple co-precipitation procedure, and its properties and synthesis conditions were thoroughly characterized and optimized. A unique “off-on-off” fluorescent response was observed when the probe sequentially interacted with Al3+ and glyphosate, and the detection method based on this phenomenon was established. The limits of detection for Al3+ and glyphosate were determined as 0.03 μmol/L and 0.03 mg/L, respectively, with rapid detection periods of one minute and four minutes. The LDH-SA/Al3+ complex requires Al3+ to generate a chelation-gathered fluorescence effect, which is the mechanism by which it quenches LDH-SA. This is possible due to the inhibition of excited-state intramolecular proton transfer and photoinduced electron transfer processes within LDH-SA after incorporating Al3+. Upon interaction with glyphosate, competitive complexation between glyphosate and Al3+ is initiated, which leads to a recovery of the fluorescence spectrum of LDH-SA and demonstrating the “off-on-off” behavior. An “INHIBIT” logic gate system was devised utilizing the response, indicating potential applications in fluorescence-based devices. Such a rapid, sequential detection capacity is impressive. It attests to the utility of LDH-SA as a probe for Al3+ or glyphosate, and suggests promise for applications in pollutant analysis or environmental monitoring applications.

Fluorescent columnar liquid crystals based on BTD hexacatenars with salicylaldimine and benzaldimine core: Self-assembly and multifunctional properties

Two series of hexacatenars SB/n and BB/n containing a benzothiadiazole (BTD) central core with triple alkyl chains at both ends via salicylaldehyde or benzaldehyde derivated Schiff base links, respectively, were prepared. Different Schiff base links lead to different self-assembly and photophysical behaviors. Both series can self-assemble into columnar liquid crystal (LC) phases but with different lattices (p6mm for SB/n, p4mm for BB/n) in bulk states, and SB/n can additionally form gels in organic solution. Interestingly, SB/n series were characterized with excited state intramolecular proton transfer (ESIPT) and aggregation-induced emission enhancement (AIEE) effects, and displayed high fluorescence in their solid, LC and gel states with large Stokes shifts and environmental sensitive unique spectra patterns. The effect of photoisomerization driven by ESIPT process on LC state of SB/n was observed. The applications of SB/n as fingerprint imaging device, Al3+ fluorescence chemosensor, white light emitting diodes (WLED) as well as light-emitting liquid crystal displays (LE-LCD) have been successfully realized.

Nuclear Quantum Effects on Nonadiabatic Dynamics of a Green Fluorescent Protein Chromophore Analogue: Ring-Polymer Surface-Hopping Simulation.

Herein, we have used the "on-the-fly" ring-polymer surface-hopping simulation method with the centroid approximation (RPSH-CA), in combination with the multireference OM2/MRCI electronic structure calculations to study the photoinduced dynamics of a green fluorescent protein (GFP) chromophore analogue in the gas phase, i.e., o-HBI, at 50, 100, and 300 K with 1, 5, 10, and 15 beads (3600 1 ps trajectories). The electronic structure calculations identified five new minimum-energy conical intersection (MECI) structures, which, together with the previous one, play crucial roles in the excited-state decay dynamics of o-HBI. It is also found that the excited-state intramolecular proton transfer (ESIPT) occurs in an ultrafast manner and is completed within 20 fs in all the simulation conditions because there is no barrier associated with this ESIPT process in the S1 state. However, the other excited-state dynamical results are strongly related to the number of beads. At 50 and 100 K, the nuclear quantum effects (NQEs) are very important; therefore, the excited-state dynamical results change significantly with the bead number. For example, the S1 decay time deduced from time-dependent state populations becomes longer as the bead number increases. Nevertheless, an essentially convergent trend is observed when the bead number is close to 10. In contrast, at 300 K, the NQEs become weaker and the above dynamical results converge very quickly even with 1 bead. Most importantly, the NQEs seriously affect the excited-state decay mechanism of o-HBI. At 50 and 100 K, most trajectories decay to the S0 state via perpendicular keto MECIs, whereas, at 300 K, only twisted keto MECIs are responsible for the excited-state decay. The present work not only comprehensively explores the temperature-dependent photoinduced dynamics of o-HBI, but also demonstrates the importance and necessity of NQEs in nonadiabatic dynamics simulations, especially at relatively low temperatures.

Amination and Protonation Facilitated Novel Isoxazole Derivative for Highly Efficient Electron and Hole Separation.

It is of great importance to understand the intrinsic relationship between phototautomerization and photoelectric properties for the exploration of novel organic materials. Here, in order to chemically control the protonation process, the aminated isoxazole derivative (2,2'-(isoxazolo[5,4-d]isoxazole-3,6-diyl)dibenzenaminium, DP-DA-DPIxz) with -N═ as the proton acceptor was designed to achieve the twisted intramolecular charge transfer (TICT) state which was triggered by an excited-state intramolecular proton transfer (ESIPT) process. This kind of protonation enhanced the intramolecular hydrogen bonding, conjugative effect, and steric hindrance effects, ensuring a barrierless spontaneous TICT process. Through the intramolecular proton transfer, the configuration torsion and conjugation dissociation of the DP-DA-DPIxz molecule was favored, which led to efficient charge separation and remarkable variations in light-emitting properties. We hope the present investigation will provide a new approach to design novel optoelectronic organic materials and shine light on the understanding of the charge transfer and separation process in molecular science.

Modulating the ESIPT Mechanism and Luminescence Characteristics of Two Reversible Fluorescent Probes by Solvent Polarity: A Novel Perspective.

As reversible fluorescent probes, HTP-1 and HTP-2 have favourable applications for the detection of Zn2+ and H2S. Herein, the impact of solvent on the excited-state intramolecular proton transfer (ESIPT) of HTP-1 and HTP-2 was comprehensively investigated. The obtained geometric parameters and infrared (IR) vibrational analysis associated with the intramolecular hydrogen bond (IHB) indicated that the strength of IHB for HTP-1 was weakened in the excited state. Moreover, structural torsion and almost no ICT behaviour indicated that the ESIPT process did not occur in HTP-1. Nevertheless, when the 7-nitro-1,2,3-benzoxadiazole (NBD) group replaced the H atom, the IHB strength of HTP-2 was enhanced after photoexcitation, which inhibited the twisting of tetraphenylethylene, thereby opening the ESIPT channel. Notably, hole-electron analysis and frontier molecular orbitals revealed that the charge decoupling effect was the reason for the fluorescence quenching of HTP-2. Furthermore, the potential energy curves (PECs) revealed that HTP-2 was more inclined to the ESIPT process in polar solvents than in nonpolar solvents. With a decrease in solvent polarity, it was more conducive to the ESIPT process. Our study systematically presents the ESIPT process and different detection mechanisms of the two reversible probe molecules regulated by solvent polarity, providing new insights into the design and development of novel fluorescent probes.

Detection mechanism of glutathione by off–on fluorescent probe based on excited state intramolecular proton transfer

The mechanism of Glutathione detection probes 2-(benzo[d]thiazol-2-yl)-6-formyl-4-methylphenyl 2,4-dinitrobenzenesulfonate (BTFMD) and BTFM-OH have been investigated. The analysis of structural parameters, interaction region indicator (IRI) value and infrared vibration spectra show the hydrogen bond is strengthened in the S1 state, which is beneficial to excited state intramolecular proton transfer (ESIPT). Combined with hole electron analysis and frontier molecular orbitals (FMOs), the electron density of BTFMD is transferred from benzothiazole and 5-methylsalicylaldehyde to 2,4-dinitrobenzenesulfonyl and the fluorescence properties changed due to photoinduced electron transfer (PET). The potential energy curve explains the single fluorescence emission and the ESIPT process in the S1 state.

Study on ESIPT process of fluorescence probe BT-ITC for detecting H2S in DMF/H2O mixed solution

A probe molecule named BT-ITC with an isothiocyanate group was synthesized and evaluated for its H2S sensing ability based on the excited state intramolecular proton transfer (ESIPT) process J K Kim, S Y Bong, R Park, J Park, D Ok Jang 2022 An ESIPT-based fluorescent turn-on probe with isothiocyanate for detecting hydrogen sulfide in environmental and biological systems, Spectrochimica Acta Part A 278 121333. The BT-ITC molecule has a large Stokes shift, short response time, and low detection limit. The end result of the reaction between the molecules BT-ITC and H2S is the BTC-NH2 molecule. The hydrogen bond of the Enol structure BTC-NH2 molecule in excited-state (S1 state) is strengthened, compared to the ground-state (S0 state). The calculated absorption and fluorescence spectra were in good agreement with the experimental values. The frontier molecule orbitals (FMOs), the potential energy curve (PEC), and scatter plots of reduced density gradient (RDG) were calculated. According to aforementioned, it was discovered that the charges of BTC-NH2 molecule were rearranged via an electron transition brought on by photoexcitation. This changes the acidity and alkaline of the proton donor and acceptor, and thus promotes the ESIPT process.

TDDFT Study on the ESIPT Properties of 2-(2'-Hydroxyphenyl)-Benzothiazole and Sensing Mechanism of a Derived Fluorescent Probe for Fluoride Ion.

The level of fluoride ions (F-) in the human body is closely related to various pathological and physiological states, and the rapid detection of F- is important for studying physiological processes and the early diagnosis of diseases. In this study, the detailed sensing mechanism of a novel high-efficiency probe (PBT) based on 2-(2'-hydroxyphenyl)-benzothiazole derivatives towards F- has been fully investigated based on density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. F- attacks the O-P bond of PBT to cleavage the dimethylphosphinothionyl group, and the potential products were evaluated by Gibbs free energy and spectroscopic analyses, which ultimately identified the product as HBT-Enol1 with an intramolecular hydrogen bond. Bond parameters, infrared vibrational spectroscopy and charge analysis indicate that the hydrogen bond is enhanced at the excited state (S1), favoring excited state intramolecular proton transfer (ESIPT). The mild energy barrier further evidences the occurrence of ESIPT. Combined with frontier molecular orbital (FMO) analysis, the fluorescence quenching of PBT was attributed to the photoinduced electron transfer (PET) mechanism and the fluorescence turn-on mechanism of the product was attributed to the ESIPT process of HBT-Enol1.

Photophysical Properties of (E)-1-(4-(Diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide Compound and Its Triple Fluorescence Emission Mechanism: A Theoretical Perspective.

In view of the application prospects in biomedicine of (E)-1-(4-(diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide (DAHTS), the behavior of excited-state dynamics and photophysical properties were studied using the density functional theory/time-dependent density functional theory method. A series of studies indicated that the intramolecular hydrogen-bond (IHB) intensity of DAHTS was enhanced after photoexcitation. This was conducive to promoting the excited-state intramolecular proton-transfer (ESIPT) process. Combining the analysis of the IHB and hole-electron, it revealed that the molecule underwent both the ESIPT process and the twisted charge-transfer (TICT) process. Relying on exploration of the potential energy surface, it was proposed that the different competitive mechanisms between the ESIPT and TICT processes were regulated by solvent polarity. In acetonitrile (ACN) solvent, the ESIPT process occurred first, and the TICT process occurred later. In contrast, in the CYH solvent, the molecule first underwent the TICT process and then the ESIPT process. Furthermore, we raised the possibility that the TICT behavior was the cause of weak fluorescence emission for the DAHTS in CYH and ACN solvents. By the dimer correlation analysis, the corresponding components of triple fluorescence emission were clearly assigned, corresponding to the monomer, dimer, and ESIPT isomer in turn. Our work precisely elucidated the photophysical mechanism of DAHTS and the attribution of the triple fluorescence emission components, which provided valuable guidance for the development and regulation of bioactive fluorescence probes with multiband and multicolor emission characteristics.

Dual detection of Hg2+ and Pb2+ by a coumarin-functionalized Schiff base in environmental and biosystems

Fluorescent chemosensors are often preferred for tracking toxic ions because of their non-destructive measurement and ease of use in environmental real samples and biosystems. Exploring high selectivity, great sensitivity, and biocompatible fluorophores with facile, accessible and dual-responsive features is currently highly demanding. A coumarin-based naphthol hydrazone Schiff base chemosensor, NaChro, is designed and synthesized in a two-step process to detect toxic metal ions with strong emission. Fluorescence spectra analysis demonstrates that the probe binds to Hg2+ and Pb2+ ions with a 1:1 and a 2:1 stoichiometry, respectively, with high sensitivity, short response time and minimal interference from other metal ions. The observed reversible turn-on reaction was attributed to the inhibition of C = N isomerization and excited-state intramolecular proton transfer (ESIPT) processes once the ions were introduced. The practical applications of NaChro are successfully addressed in paper strips, various water samples, HeLa cells and Zebrafish, demonstrating that the probe can detect and track Hg2+ and Pb2+ ions in environmental samples and biosystems.

TADF Regulation by Tuning Keto‐Energy Levels, ISC/RISC Equilibrium in Coordination Polymers with Excited State Intramolecular Proton Transfer (ESIPT)

AbstractThermally activated delayed fluorescence (TADF) and long persistent luminescence (LPL) are emerging photophysical hotspots, which involve the singlet/triplet excited states and two‐way energy transfer processes between them via intersystem crossing (ISC) or reverse intersystem crossing (RISC). Herein, a new tactic is reported for the regulation of keto‐energy levels and ISC/RISC equilibrium via the introduction of electron‐withdrawing fluorine in a series of excited state intramolecular proton transfer (ESIPT) ligands and corresponding Cd(II) coordination polymers. Among them, the fluorine p‐substituted to the hydroxy group along the nodal plane on the phenol site improves the thermodynamic stability of the keto‐isomers of the ligand, thereby lowering the keto‐energy level and promoting the ESIPT process effectively. Uniquely, the lower‐energy keto excited state makes the ISC/RISC equilibrium shift to the direction of RISC progress, and thus arousing efficient TADF in the constructed coordination polymer. A comprehensive transient photophysical and theoretical study verifies the greatly promoted RISC progress, rather than suppressed ISC is aroused in the p‐substituted system, suggesting a clear‐cut strategy in the design of coordination polymers with good TADF performance.

Crystal structure, tautomerism and photostability of 2-(2-pyridyl)-phenalene-1,3-dione

Tautomerism of cyclic β-diketones has been of scientific interest for decades due to the practical applications it can render, from sensors to photostable materials. In this work the tautomerism of 2-(2-pyridyl)-phenalene-1,3-dione (PPD) was studied in solid state, in solution, and in gas phase through a combination of experimental and theoretical methods. Single-crystal X-ray diffraction analysis of PPD revealed its existence in diketo form in the solid state with protonated pyridyl nitrogen that is stabilized by the intramolecular hydrogen bond of N-H···O type. A very large Stokes shift was observed in the emission spectra in DMSO (ca. 177 nm) and in ethanol (ca. 160 nm), indicating on possible excited-state intramolecular proton transfer (ESIPT) process. DFT calculations in ground state (gas phase and water medium) and in the excited singlet state (B3LYP-6311++G(d,p)) agree very well with the experimental data and suggest reverse order of the possible OH and NH tautomers in the ground and the excited singlet state, namely the diketo NH tautomer is the most stable one in the ground state whereas in the excited singlet state the enol OH form is more stable. The photostability of PPD was estimated by irradiation experiments that were performed in comparison with 2-acetylindan-1,3-dione (2AID), which is a compound with proven high photostability in ethanol and fast ESIPT. The data showed that unlike 2AID, the 2-(2-pyridyl)-phenalene-1,3-dione exhibits lower photostability in ethanol. These results could suggest that either the ESIPT process is not the only transformation that takes place in the excited state of PPD, or it is not as fast as the one of 2AID.

Fluorescence enhancement mechanism of new 4-Cyanobiphenyl-based schiff base probe by coordination interaction with cadmium ion

In this research, we focus on the theoretical exploration of the fluorescent process and sensing mechanism for Cd2+ of a novel Schiff base probe BPC based on 4-Cyanobiphenyl [Journal of Luminescence, 249, (2022), 119,017.]. The proton transfer process of BPC is investigated by constructing potential energy curves of the ground (S0) and excited singlet (S1) states with the extended O1–H2 distance. In S1 state, the probe BPC, in addition to the excited state intramolecular proton transfer (ESIPT) process, is found to undergo a CN isomerization process by rotating the dihedral angle C2–C3N3–C4. Meanwhile, a non-emissive state in BPC is found in our work. The weak fluorescence phenomenon observed in experiment is caused by the CN isomerization product of BPC. Upon the addition of Cd2+, BPC can coordinate with Cd2+, which prevents CN isomerization and ESIPT processes from occurring and turns on the intense fluorescence emission. This study clarifies sensing mechanism of BPC for detecting Cd2+ based on the inhibition of ESIPT and CN isomerization processes, which paves the way for the further development of new fluorescent probes for metal ions in the future.

Unlocking the potential of solvent polarity in directing ESIPT pathways of HHMB with dual hydrogen bond acceptors: a DFT/TD-DFT study

The excited-state intramolecular proton transfer (ESIPT) process involving dual hydrogen bond acceptors (HBAs) is of great interest in research and has significant potential for applications due to its flexible adjustability. In this work, the solvent polarity-dependent changes in structures, photophysical properties and ESIPT processes of 2-(2-hydroxy-3-hydroxyiminomethyl-5-methylphenyl)-benzimidazole (HHMB) with two asymmetric HBAs are investigated. Firstly, the orientation of intramolecular hydrogen bond (IHB) under different solvent polarities are explored. The computational results indicate that in non-polar solvents, the central hydroxyl group predominantly forms an IHB with the imine of the oxime group, resulting in large Stokes and near-infrared emission peaks. Conversely, in polar solvents, the central hydroxyl group links the imidazole group to form a stronger IHB with improved fluorescence efficiency. Additionally, the quantum chemical calculations are used to simulate the absorption–emission spectra and plot the frontier molecular orbitals, as well as the potential energy curves about ESIPT in different solvents. In conclusion, we elucidate the rationale behind the preferential formation of the biased IHBs and examine its impact on the ESIPT process by manipulating the solvent polarity. Theoretical studies on the dual HBAs molecule, exhibiting specific selectivity, pave the way for the development of higher-performance fluorescence probes and luminescent materials.

Excited-state dynamics of 4-hydroxyisoindoline-1,3-dione and its derivative as fluorescent probes.

Fluorescent probes have become promising tools for monitoring the concentration of peroxynitrite, which is linked to many diseases. However, despite focusing on developing numerous peroxynitrite based fluorescent probes, limited emphasis is placed on their sensing mechanism. Here, we investigated the sensing mechanism of a peroxynitrite fluorescent probe, named BHID-Bpin, with a focus on the relevant excited state dynamics. The photoexcited BHID-Bpin relaxes to its ground state via an efficient nonradiative process (∼300 ps) due to the presence of a minimum energy conical intersection between its first excited state and ground state. However, upon reacting with peroxynitrite, the Bpin moiety is cleaved from BHID-Bpin and BHID is formed. The formed BHID exhibits strong dual band fluorescence which is caused by an ultrafast excited-state intramolecular proton transfer process (∼1 ps).

Excited-state dynamics of 3-hydroxychromone in gas phase.

In recent years, 3-hydroxychromone (3-HC) and its derivatives have attracted much interest for their applications as molecular photoswitches and fluorescent probes. A clear understanding of their excited-state dynamics is essential for their applications and further development of new functional 3-HC derivatives. However, the deactivation mechanism of the photoexcited 3-HC family is still puzzling as their spectral properties are sensitive to the surrounding medium and substituents. The excited-state relaxation channels of 3-HC have been a matter of intense debate. In the current work, we thoroughly investigated the excited-state decay process of the 3-HC system in the gas phase using high-level electronic structure calculations and on-the-fly excited-state dynamic simulations intending to provide insight into the intrinsic photochemical properties of the 3-HC system. A new deactivation mechanism is proposed in the gas phase, which is different from that in solvents. The excited-state intramolecular proton transfer (ESIPT) process that occurs in solutions is not preferred in the gas phase due to the existence of a sizable energy barrier (∼0.8 eV), and thus, no dual fluorescence is found. On the contrary, the non-radiative decay process is the dominant decay channel, which is driven by photoisomerization combined with ring-puckering and ring-opening processes. The results coincide with the observations of an experiment performed in a supersonic jet by Itoh (M. Itoh, Pure Appl. Chem., 1993, 65(8), 1629-1634). The current work indicates that the solution environment plays an important role in regulating the excited-state dynamic behaviour of the 3-HC system. This study thus provides theoretical guidance for the rational design and improvement of the photochemical properties of the 3-HC system and paves the way for further investigation into its photochemical properties in complex environments.

Effects of substitution and conjugation on photophysical properties of ESIPT-based fluorophores with the core of 4-aminophthalimide

4-Aminophthalimide is a highly fluorescent signaling unit with excellent photophysical properties and wide application foregrounds. Based on this, a range of theoretical investigations are conducted on the fluorescent probe (E)-5-((2-hydroxybenzylidene) amino) isoindoline-1, 3-dione (HID) with the core of 4-aminophthalimide using density functional theory (DFT) and time-containing density functional theory (TD-DFT) methods in this paper. The optimized configurations, vertical excitation and emission energies, electronic characteristics and excited-state intramolecular proton transfer (ESIPT) behaviors of the probe HID are discussed in detail. Furthermore, to enhance the luminescent properties of HID, five novel compounds have been designed based on the structure of HID by introducing amino, methoxy and naphthalene groups (–NH2, –OMe and C10H8). Our work thoroughly explores how the property and position of substituents and conjugation affect photophysical characteristics and ESIPT processes. We find that the ESIPT dynamics can be modulated by the substitution and conjugation effects. Specifically, the introduction of amino and methoxy groups at the ortho-position and the introduction of the naphthalene group promote the ESIPT behavior of HID1, whereas the introduction of amino and methoxy groups at the meta-position exhibits the contrary impact. Therefore, we boldly infer that the introduction of electron-donating groups in the ortho-position and the introduction of the conjugated group make the ESIPT process more effortless to occur, whereas the introduction of substituents with opposing natures in the meta-position makes the ESIPT process more difficult to occur. In addition, the ionization potentials (IP), electron affinities (EA) and reorganization energies (λh and λe) of molecules are calculated to assess their potential as luminescent materials. Our work not only reveals the luminescence and ESIPT mechanism of the probe HID1, but also proposes to modulate the ESIPT process through the substitution and conjugation effects. In particular, the designed molecules have better photoelectric properties as a result of their red-shifted absorption and fluorescence spectra, smaller energy gaps, larger transferred charges and greater charge transferred distances, which offers some valuable ideas for the experimental development of more efficient organic luminescent materials with ESIPT properties.

Reversible ratiometric fluorescence probe for the detection of HClO/H2S based on excited state intramolecular proton transfer mechanism

The redox balance between HClO and H2S is essential for the physiological and pathological properties of organisms. Therefore, monitoring the redox process between HClO and H2S is of great significance. Shen et al. synthesised a reversible ratiometric fluorescence probe BT-Se based on excited state intramolecular proton transfer (ESIPT) reaction for the detection of HClO and H2S in previous experiments. When BT-Se detects HClO, it will be oxidised to a new substance which is named BT-SeO, and BT-SeO can be reduced to BT-Se by detecting H2S. BT-Se and BT-SeO emit different colours of fluorescence to realise detection. In this paper, the attribution of the fluorescence peak and the luminescence mechanism are studied. The bond parameters, infrared (IR) vibrational frequency, interaction region indicator (IRI) and the potential energy curve are analysed to demonstrate that the excited state is easier to conduct the ESIPT process. The combination of frontier molecular orbitals (FMOs) and hole–electron analysis reveals the charge excitation characteristics. This work suggests that the yellow and blue fluorescence observed in the experiment is emitted by the keto structures of BT-Se and BT-SeO, respectively. Our research will provide an important theoretical basis for the detection of photophysical phenomena in reversible ratiometric fluorescent probes.

Two wavelength band emission WGM lasers via photo-isomerization

Abstract Wavelength switchable microcavity is indispensable component for various integrated photonic devices. However, achieving two wavelength band emission of the whispering gallery mode (WGM) laser is challenging. Here, we propose a strategy to realize two wavelength band emission WGM lasers activated by photo-isomerization based on excited-state intramolecular proton transfer (ESIPT) process in isolated/coupled polymer microfiber cavities. The WGM microcavity is built by highly polarized organic intramolecular charge-transfer (ICT) dye molecules. The two cooperative gain states of ICT dye molecules can be controlled by optimizing energy levels. Thereby, the lasing wavelength can be reversibly switched under photo-isomerization activated in the ESIPT energy-level progress. The photonic bar code can be generated by following the strategy of proposed design. This work provides a promising route to achieve switchable WGM laser in on-chip photonic integration.