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In this work, an innovative route for upgrading biomass-derived phenolic monomers by “hydrogen-free” hydrodeoxygenation (HDO) was proposed and evaluated.

The water-splitting reaction using photocatalyst particles is a promising route for solar fuel production

Excited-state intramolecular proton transfer (ESIPT) is favored by researchers because of its unique optical properties. However, there are relatively few systematic studies on the effects of changing the electronegativity of atoms on the ESIPT process and photophysical properties. Therefore, we selected a series of benzoxazole isothiocyanate fluorescent dyes (2-HOB, 2-HSB, and 2-HSeB) by theoretical methods, and systematically studied the ESIPT process and photophysical properties by changing the electronegativity of chalcogen atoms. The calculated bond angle, bond length, energy gap, and infrared spectrum analysis show that the order of the strength of intramolecular hydrogen bonding of the three molecules is 2-HOB2-HSB>2-HSeB. In addition, the calculated electronic spectrum shows that as the atomic electronegativity decreases, the emission spectrum has a redshift. Therefore, this work will offer certain theoretical guidance for the synthesis and application of new dyes based on ESIPT properties.

Interpreting the initial decomposition mechanism is important for evaluating the thermal stability of explosives. In this study, we theoretically investigated the initial thermal decomposition reactions for two typical energetic materials, FOX-7 and RDX, in both the gas phase and crystal phase. Single molecular decomposition pathways in the gas phase are calculated using the density functional theory (DFT) method, and the crystal phase reactions are simulated through the MM/DFT-based ONIOM method. The calculation results indicate that the crystal environment has a significant influence on the initial thermal decomposition mechanism of FOX-7 and RDX. The cage effect induced by the crystal environment greatly confines molecular mobility and diffusion, rendering the generated small molecules to react with the remaining fragment and yield new decomposition channels compared with the gas phase condition. The crystal packing structures and intermolecular interactions (hydrogen bonds/π-π stacking) significantly increase the reaction barriers of FOX-7 and RDX, leading to the crystal phase reactions being more difficult to occur than in the gas phase. Since the practical application of explosives is mostly in the crystal state, it is important to consider the environmental effects on the initial decomposition reactions. The same insight can also be relevant for other energetic materials.

A key process underlying the application of low-dimensional, quantum-confined semiconductors in energy conversion is charge transfer from these materials, which, however, has not been fully understood yet. Extensive studies of charge transfer from colloidal quantum dots reported rates increasing monotonically with driving forces, never displaying an inverted region predicted by the Marcus theory. The inverted region is likely bypassed by an Auger-like process whereby the excessive driving force is used to excite another Coulomb-coupled charge. Herein, instead of measuring charge transfer from excitonic states (coupled electron-hole pairs), we build a unique model system using zero-dimensional quantum dots or two-dimensional nanoplatelets and surface-adsorbed molecules that allows for measuring charge transfer from transiently-populated, single-charge states. The Marcus inverted region is clearly revealed in these systems. Thus, charge transfer from excitonic and single-charge states follows the Auger-assisted and conventional Marcus charge transfer models, respectively. This knowledge should enable rational design of energetics for efficient charge extraction from low-dimensional semiconductor materials as well as suppression of the associated energy-wasting charge recombination., Marcus inverted region for charge transfer from low-dimensional semiconductor materials has been long sought after. Here, the authors reveal this region by directly measuring charge transfer from single-charge states rather than excitonic states.

Two-dimensional (2D) photocatalytic material is a vital project for modern solar energy conversion and storage. Despite a vast family of potential 2D photocatalysts that is demonstrated, their commercial applications are severely limited because of fast photogenerated electron-hole recombination. Here, based on first-principles, we propose a general paradigm to boost the separation of photoexcited charge carriers in 2D photocatalysts by stacking engineering. Taking the emerging water splitting photocatalyst MoSi2N4 as an example, we show that specific interlayer stacking-induced electric polarization plays a significant role in altering the electronic properties and thus the suppressed recombination rate of photoexcited carriers. Moreover, we find that the catalytic performance can be further controlled by vertical strain. These generalized findings not only highlight the importance of stacking-induced electric polarization but also offer new prospects for the design and application of 2D photocatalysts.

Summary The ingenious construction of electron donor-acceptor (D-A) systems has been proven to be the major trend for advanced performance optoelectronic materials. However, the related development is undiversified and has become stereotyped in recent years, and the explorations of innovative architecture with both prominent optoelectronic properties and innovatively coined optoelectronic mechanisms are appealing, yet significantly challenging tasks. Here, we exploit a series of unique Janus luminogens, namely TAOs, with unique charge separation in a simple five-membered mesoionic ring. TAOs, having low molecular weight (∼329 g mol−1), present efficient aggregation-induced red/near-infrared emission (550–850 nm) with up to 21.5% of fluorescence quantum yield. An original mechanism, termed bended intramolecular charge transfer (BICT), is proposed to understand the fluorescence behavior. It is experimentally demonstrated that TAOs exhibit great potential for use as molecular transistors and can be efficiently utilized in living cells, bacteria, and brain imaging in a straightforward manner by using intravenous postinjection with outstanding photostability and biocompatibility.

Lead-free halide perovskites have triggered interest in the field of optoelectronics and photocatalysis because of their low toxicity, and tunable optical and charge-carrier properties. From an application point of view, it is desirable to develop stable multifunctional lead-free halide perovskites. We have developed a series of Cs2 Ptx Sn1-x Cl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2 Ptx Sn1-x Cl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2 Ptx Sn1-x Cl6 solid solution with a small amount of Pt4+ substitution exhibits photocatalytic hydrogen evolution activity. An optical spectroscopy study reveals that the switch between photoluminescence and photocatalysis functions is controlled by sub-band gap states. Our finding provides a new way to develop lead-free multifunctional halide perovskites with high stability.

Highly efficient triplet photosensitizers (PSs) have attracted increasing attention in cancer photodynamic therapy where photo-induced reactive oxygen species (ROSs, such as singlet oxygen) are produced via singlet–triplet intersystem crossing (ISC) of the excited photosensitizer to kill cancer cells. However, most PSs exhibit the fatal defect of a generally less-than-1% efficiency of ISC and low yield of ROSs, and this defect strongly impedes their clinical application. In the current work, a new strategy to enhance the ISC and high phototherapy efficiency has been developed, based on the molecular design of a thio-pentamethine cyanine dye (TCy5) as a photosensitizer. The introduction of an electron-withdrawing group at the meso-position of TCy5 could dramatically reduce the singlet–triplet energy gap (ΔEst) value (from 0.63 eV to as low as 0.14 eV), speed up the ISC process (τISC = 1.7 ps), prolong the lifetime of the triplet state (τT = 319 μs) and improve singlet oxygen (1O2) quantum yield to as high as 99%, a value much higher than those of most reported triplet PSs. Further in vitro and in vivo experiments have shown that TCy5-CHO, with its efficient 1O2 generation and good biocompatibility, causes an intense tumor ablation in mice. This provides a new strategy for designing ideal PSs for cancer photo-therapy., The electron-withdrawing group at the meso-position of Thio-Cy5 could dramatically reduce the singlet–triplet energy gap, and speed up the intersystem crossing process.

The imaging of hypoxia in tumors by metal-free organic phosphors has long been a challenge due to the lack of molecules capable of phosphorescing efficiently in their dilute solutions. Herein, a new strategy for designing phosphorescent molecules was provided by building selenium-based intramolecular charge transfer systems to address this issue. The results showed that molecules based on this strategy exhibited efficient phosphorescence even in solutions, showed very low cytotoxicity to cells and can be successfully applied to image hypoxia in cells and tumors. In addition, the mechanism responsible for the efficient phosphorescence was investigated by the combination use of transient absorption spectra and theoretical calculations.

As a special fluorescence phenomenon, double fluorescence has been widely developed and applied in various fields. Nevertheless, most of the research of fluorescence emission channel stay in the first excited state, research on how to control the fluorescence emission channel through the upper excited state is relatively underexplored. Here, we use the time-dependent density functional theory method and take the 2-(2’-hydroxyphenyl) benzoxazole (HBO) derivatives system as an example to study the effect of upper excited states on the double fluorescence. The calculation results show that a new mechanism for the dual fluorescence was proposed, which involved the different decay pathways from upper excited-state, the internal conversion through vibrational relaxation and conical intersection, respectively. This research has potential value and will help how to control the fluorescence emission channel through the upper excited state.

The fluorescence of most organic chromophore is emitted from the ππ* state, whereas the nπ* state, as a dark state, plays an important role in quenching the fluorescence when its energy is close to the ππ* state. Herein, we report a theoretical study on the fluorescence quenching of 8-methoxy-4-methyl-2H-benzo[g]chromen-2-one by the nπ* state and propose a new mechanism for describing the vibronic coupling between the ππ* and nπ* states. By applying extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2) to optimize the geometries, the geometry distortion of the ππ* state along the out-of-plane mode is observed. This geometry distortion causes the stretching vibration of the carbonyl group to be coupled with the C-C bonds of the pyran ring, which become a Franck-Condon active mode upon photoexcitation and provides a driving force for nonradiative decay from the nπ* state, even if it is energetically unfavorable. This mechanism is significantly different from the previously proposed "proximity effect" and cannot be captured by the popularly used time-dependent density functional theory (TDDFT) and complete-active-space self-consistent field (CASSCF) methods.

It is a challenge to rationally design an organic molecule with thermally activated delayed fluorescence (TADF) due to the intrinsically spin-forbidden transition. Meanwhile, those reported TADF organic molecules have difficulty to be directly applied in the field of biological and medical imaging because they usually have no water solubility. Here, a water-soluble TADF organic molecule DCF-BXJ was developed by introducing a flexible propenyl group into the commercial traditional fluorophore DCF (2,7-dichlorofluorescein). The flexible group provides nonradiative rotational motion, which causes an efficient energy level cross between the S1 state and the T2 state of DCF-BXJ. Results of transient absorption spectra and theoretical calculations supported that nonradiative rotational motion of the flexible group can enhance intersystem crossing (ISC) and bring out TADF. This work provides a new mechanism explanation for TADF existing in organic molecules.

The twisted intramolecular charge transfer has been proposed for a number of years and widely accepted to explain the excited-state dynamics of organic molecules. Recently, a new state termed as "twisted and rehybridized intramolecular charge transfer" has been proposed to explain the excited-state dynamics of an aniline-triazine electron donor-acceptor dyad with an alkyne spacer based on ultrafast time-resolved spectroscopy. However, the change of the geometries along the excited-state decay pathway remains unknown. In this study, by optimization of the excited-state geometry of the donor-acceptor dyad and potential energy surface scan along the twisting angle, we successfully reproduce the experimentally observed band in time-resolved infrared absorption spectroscopy. Our calculation results demonstrated that the rehybridization process is not involved and only the twisted intramolecular charge transfer state is formed. Moreover, we located a minimum energy conical intersection between the ground and first excited-state of the donor-acceptor dyad, which is easily reached and corresponding to the primary nonradiative decay pathway of the donor-acceptor dyad. The energy of minimum energy conical intersection is solvent-dependent and consistent with the experimentally observed solvent-dependent lifetime of excited state.

As one of the most important energetic material molecules, hexanitrohexaazaisowurtzitane (CL-20) can only be synthesized using an amine with a benzyl group. Moreover, the reaction mechanism remains unexplored and the special role of the benzyl group has not been revealed. To address these issues, we perform an extensive theoretical study to investigate the synthesis mechanism of CL-20 precursor HBIW by employing density functional theory. Our calculated results demonstrate that the benzyl group can reduce the energy of the intermediate and the energy barrier of the rate-determining step due to the π-π stack interaction between two benzene rings of the benzyl group. For the first time, we revealed that the reactions can produce 16 intermediates with different chiralities during the formation of the first two side five-membered rings and only two of which can further form the bottom six-membered ring and finally obtain the product HBIW. The steric hindrance effect of the benzyl group leads to the formation of a higher-energy intermediate first, thereby providing an opportunity to correct the wrong chirality. All of these factors make the diimine with the benzyl group the most suitable reactant for the synthesis of CL-20.

As a special fluorescence phenomenon, double fluorescence has been widely developed and applied in various fields. Nevertheless, most of the research on fluorescence emission channels focuses on the first excited state, while the research on how to control the fluorescence emission channel through the upper excited state is relatively under-explored. Here, we use the time-dependent density functional theory method and consider the 2-(2'-hydroxyphenyl) benzoxazole (HBO) derivative system as an example to study the effect of upper excited states on double fluorescence. According to the calculation results, a new mechanism for the dual fluorescence was proposed, which involved the different decay pathways from the upper excited-state, the internal conversion through vibrational relaxation, and conical intersection, respectively. This research has potential value and can help in determining how to control the fluorescence emission channel through the upper excited state.

1,1-diamino-2,2-dinitroethene (FOX-7) is a novel energetic material with high performance and low sensitivity. In order to deeply understand the reaction mechanism in the initiation “hot spots” of FOX-7 and reveal the growth mechanism of these initiation “hot spots” in the explosion process, the detailed mechanisms of bimolecular reaction of NO2 and FOX-7, as well as the subsequent reactions have been investigated by the quantum chemical calculations. The mechanism of NO2 and FOX-7 bimolecular reaction and the catalytic effect of NO2 were revealed by three key dissociation paths. It is demonstrated that the NO2 molecule plays an important role in promoting the decomposition of the FOX-7 molecule, and the main exothermic pathways were the reactions between oxidizing intermediates (NO, NO2), and reducing intermediates (CO, NH3).

In this article, we propose a new excited state dynamics mechanism for quinoline-pyrazole isomers (QP-1 and QP-2) in the liquid phase based on the time-dependent density functional theory (TD-DFT) method. The calculated potential energy curve shows that QP-2 is more likely to occur as an excited state intramolecular proton-transfer (ESIPT) process than QP-1, whereas QP-2 will occur as a twisted intramolecular charge transfer (TICT) process, which is also the main decay pathway of QP-2 fluorescence quenching. The TICT process is not involved in QP-1 due to the high energy barrier. Based on excited state energy decomposition and charge decomposition analysis, it is determined that the energy gap and hole-electron interaction are the main driving forces that can cause the TICT process to occur. These results are inconsistent with the conclusions of recent theoretical reports [

Charge transfer and recombination across the inorganic/organic interface in nanocrystal or quantum dot (QD)-molecule hybrid materials have been extensively studied. Principles of controlling charge transfer and recombination via energetics and electronic coupling have been established. However, the use of electron spin to control transfer and recombination pathways in such systems remains relatively underexplored. Here we use CdS QD-alizarin (AZ) as a model system to demonstrate this principle. Using time-resolved spectroscopy, we found that the charge-separated states (QD

Very recently, the bulk synthesis of cyclo-N5– from arylpentazole through the treatment with m-chloroperbenzonic acid (m-CPBA) and ferrous bisglycinate ([Fe(Gly)2]) (Zhang, C., et al. Science 2017,...

Stimulated by the early theoretical prediction of B80 fullerene and the experimental finding of the B40 cage, the structures of medium-sized boron clusters have attracted intensive research interest during the last decade, but a complete picture of their size-dependent structural evolution remains a puzzle. Using a genetic algorithm combined with density-functional theory calculations, we have performed a systematic global search for the low-lying structures of neutral Bn clusters with n = 31-50. Diverse structural patterns, including tubular, quasi-planar, cage, core-shell, and bilayer, are demonstrated for the ground-state Bn clusters; for certain cluster sizes, unprecedented geometries are predicted for the first time. Their stabilities at finite temperatures are evaluated, and the competition mechanism between various patterns is elucidated. Chemical bonding analysis reveals that the availability of localized σ bonds and delocalized π bonds in the Bn clusters play a key role in their structural stability. Our results provide important insights into the bonding pattern and growth behavior of medium-sized boron clusters, which lay the foundation for experimental design and synthesis of boron nanostructures.

Although the restriction of intramolecular motion (RIM) has been accepted as a general working mechanism for the aggregation-induced emission (AIE) phenomenon, some new mechanisms, such as suppression of Kasha's rule (SOKR), has also been proposed to explain the AIE of boron difluorohydrazone (BODIHY) derivatives. However, the understanding of the relation and difference between RIM and SOKR mechanisms is limited. To address this issue, we performed a theoretical study on the excited state decay of a series of BODIHY derivatives. Surprisingly, we found that the first excited state of BODIHY derivatives is a bright state and contradicts with the SOKR mechanism. Importantly, we proposed a new mechanism, termed as restriction of flip-flop motion, to explain the AIE of BODIHY derivatives. This mechanism involves the formation of an umbrella-like minimal energy conical intersection through flip-flop motion, which is easily accessible in low-viscosity solvents and will be restricted in high-viscosity solvents.

It is of high importance to develop high-efficient chemosensors for explosive nitroaromatics and explore their sensing mechanisms. In this work, the sensing mechanisms of a series of arylene-vinylene terpyridine conjugated fluorescent probes (P1-P4) for TNP have been investigated in depth. The optical discrepancy of P4 is attributed to the different electron excitation distribution caused by the strong intramolecular twist. The rational combination complex has been proposed and further confirmed with Gibbs free energy profile and 1H NMR analysis. Frontier molecular orbitals (FMOs) analysis demonstrates that photo-induced electron transfer (PET) is the fluorescence quenching mechanism for the TNP detection.

In the present contribution we carried out a TDDFT and femtosecond transient absorption study of the excited state dynamics of TNT in DMSO solvent. Vertical excitation and excited state relaxation were calculated at the SMD/M06-2X/TZVP level of theory. The electron absorption spectrum for the DMSO solvated TNT was calculated and compared with the experimental results. The results of the electronic excitation energies and the spin–orbital constants imply an intersystem crossing for the S1–T2 transition. The femtosecond time-resolved transient absorption measurements of the TNT in DMSO show the presence of two absorption signals around 650 nm and 540 nm, which are assigned to the population in the lowest singlet and triplet excited states, S1 and T1, respectively. The fast decay of the S1 state population is assigned to an efficient S1–T2 intersystem crossing, which soon internally converts to the T1 state. The slow decay of the T1 population is attributed to the nonradiative transition to the S0 state. The combined theoretical and experimental results present a mechanistic view of the photophysical dynamics of TNT in DMSO solution.

Boron-dipyrromethene derivatives (BODIPYs) are a category of molecules with excellent photophysical properties and can be applied to various fields. This work investigates the fluorescent properties of two azomethine-BODIPY dyads in different solvents based on the time-dependent density functional theory (TD-DFT) method. The potential energy curves (PECs) show that the polar protic solvent and the enhanced π-conjugation effect can lower the proton-transfer (PT) barriers, causing the main configuration of NA-BODIPY in methanol to be the keto form, while the main configuration of NA-BODIPY in toluene and SA-BODIPY in methanol and toluene is the enol form. The keto forms of the two compounds possess the twisted intramolecular charge transfer (TICT) decay pathway in the excited state identified by the optimized twisted configurations and the appropriate barriers of the TICT process, whereas the twisted configurations of the enol forms are nonexistent. TICT successfully competes with excited-state proton transfer (ESIPT) of the keto form, which leads to the fluorescence quenching of NA-BODIPY in methanol. This work provides new ideas for the influence of enol-keto tautomerism and the competitiveness of TICT and ESIPT on the photophysical properties of BODIPYs and is expected to provide guidance for the design of new BODIPY functional molecules.

Although a large number of fluorescein derivatives have been developed and applied in many different fields, the general mechanisms for tuning the fluorescence of fluorescein derivatives still remain uncovered. Herein, we found that the fluorescence quenching of neutral form of fluorescein derivatives in acidic medium resulted from a dark nπ* state, whereas the fluorescence of the anionic form of fluorescein derivatives in the gas phase and alkaline solutions was tuned by minimal energy conical intersection (MECI). The formation of MECI involved significant rotation of benzene ring and flip-flop motion of xanthene moiety, which would be restricted by intermolecular hydrogen bonding and lowering temperature. The energy barrier for reaching MECI depended on the substituents in the benzene moiety in accordance with experimentally observed substituent effects. These unprecedented mechanisms would lead to a recognition of fluorescein derivatives and could provide a correct and instructive design strategy for further developing new fluorescein derivatives.

The ingenious construction of electron donor-acceptor (D-A) system has been proven to be the major trend for novel advanced-performance optoelectronic materials. However, the related development is undiversified and become stereotyped in recent years, and the explorationsof new architecture with both prominentoptoelectronic property and innovatively coined optoelectronic mechanism are appealing yet significantly challenging tasks. We herein exploit a series of novel Janus luminogens, namely TAOs, with unique charge separation in asimple five-membered mesoionic ring.TAOs having low molecular weight present efficient aggregation-induced red/near-infrared emission with up to 21.5% of fluorescence quantum yield. A new mechanism termed as bended intramolecular charge transfer (BICT) is proposed to understand the fluorescence behavior. It is experimentally demonstrated that TAOs exhibit great potential for the use as molecular transistor, and can be efficiently utilized in brain imaging straightforwardly through intravenous postinjection.

The abnormal level of cysteine (Cys) in the human body will cause a series of diseases, and the study of the sensing mechanism is of great significance for the design of efficient fluorescent probes. Here, we used time-dependent density functional theory to study the sensing mechanism of a newly synthesized imidazo [1,5-α] pyridine-based fluorescent probe (MZC-AC) for the detection of Cys, which is proposed to be designed based on excited-state intramolecular proton transfer (ESIPT). We first show that the fluorescence quenching mechanism of MZC-AC is due to a nonclassical photoinduced electron transfer (PET) process in which the curve crossing between local excited and charge-transfer states is observed and the acrylate group acts as an electron acceptor. When the acrylate group is replaced by the hydroxyl group due to the reaction between MZC-AC and Cys, the PET is off and a significant fluorescence enhancement of the formed MZC is observed. Our theoretical results indicate that the fluorescence enhancement mechanism of MZC is not based on the ESIPT. The calculated potential energy curve along the proton transfer pathway shows that the electronic energy of MZC-keto is larger than that of MZC-enol. Moreover, the computed emission energy of MZC-enol is closer to the experimental data than that of MZC-keto. The experimentally observed large Stokes shift was ascribed to the intramolecular charge transfer character of the first excited state of MZC. Our theoretical results can explain well the fluorescence behavior of MZC-AC and MZC and invalidate the experimentally proposed ESIPT mechanism of MZC.

The biological roles of reactive oxygen species (ROS) depend highly on their dynamics. However, it has been challenging for measuring the dynamics of ROS in cells. In this study, we address a core challenge in developing fluorescence probes for monitoring ROS dynamics by designing a redox couple that can respond rapidly to both oxidation and reduction events. We show that such molecules can be designed by taking advantage of the steric effects of electron-donating groups at the ortho position relative to the selenium center. We demonstrate this design in a new fluorescence probe named Fl-Se. Results reveal that Fl-Se and its oxidized product Fl-SeO rapidly respond to HClO, an important member of the ROS family, and glutathione (GSH), with t1/2 = 2.7 ms at [HClO] = 1 μM; t1/2 = 61 ms at [GSH] = 1 mM. When applied in cells, Fl-Se satisfactorily tracks the dynamics of intracellular HClO in H2O2-stimulated HL-60 cells, as well as the different dynamic behaviors of HClO fluctuations involved in the phorbol 12-myristate-13-acetate-activated immune response of RAW264.7 cells and the 3-deazaneplanocin A-induced apoptosis of HL 60 cells.

The 8-oxo-deoxyguanosine is the most abundant specie of the DNA oxidative damage. Despite the deleterious effects such as gene mutation it may cause, the 8-oxodG was also reported to have beneficial effect such as repairing the nearby cyclobutane pyrimidine dimer (CPD) after photoexcitation. Due to its strong biological relevance, the photoinduced excited state dynamics behavior of 8-oxo-deoxyguanosine is of particular interest. In this work, a theoretical investigation by combination of complete active space self-consistent field (CASSCF) ab initio calculations and on-the-fly nonadiabatic dynamics simulations are implemented to provide intrinsic deactivation mechanism of its free base 8-oxoguanine after being excited to the S

The effects of the heteroatom and position on excited-state intramolecular proton transfer (ESIPT) of 2-[4′-(N-4,6-dichloro-1,3,5-triazi-n-2-yl)2′hydroxyphenyl]benzoxazole (4THBO) have been investigated via time-dependent density functional theory studies. The heteroatoms refer to O and S atoms, and the position effect refers to the N-4,6-trichloro-1,3,5-triazin-2-yl (TCT) substituents in the para and meta positions. The configuration of the four compounds (4THBO, 4THBT, 5THBO and 5THBT) was optimized and the bond lengths, bond angles and infrared spectra of the atoms participating in the proton transfer in the S0 and S1 states were studied. The occurrence of ultrafast ESIPT in the four compounds was demonstrated. Moreover, the potential energy curves of the S0 and S1 states were constructed, and the effects of the heteroatom substitution and substituent position changes on the ESIPT mechanism of the four 4THBO derivatives were analyzed. The results show that the ESIPT barrier of the S atom substitution in the excited state is lower than that of the O atom-substituted molecule, and the energy barrier of the substituent (TCT) in the meta-position is significantly smaller than that in the para-position. These results indicate that the substitution of the S heteroatom promotes the ESIPT of the 4THBO compound and that the substituent (TCT) in the para position is more prone to proton transfer than that in the meta position. Our work could provide a theoretical basis for further experiments.