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The quest for thermally stable energetic materials is pivotal in advancing the safety of applications ranging from munitions to aerospace. This perspective delves into the role of theoretical methodologies in interpreting and advancing the thermal stability of energetic materials. Quantum chemical calculations offer an in-depth understanding of the molecular and electronic structure properties of energetic compounds related to thermal stability. It is also essential to incorporate the surrounding interactions and their impact on molecular stability. Ab initio molecular dynamics (AIMD) simulations provide detailed theoretical insights into the reaction pathways and the key intermediates during thermal decomposition in the condensed phase. Analyzing the kinetic barrier of rate-determining steps under various temperature and pressure conditions allows for a comprehensive assessment of thermal stability. Recent advances in machine learning have demonstrated their utility in constructing potential energy surfaces and predicting thermal stability for newly designed energetic materials. The machine learning-assisted high-throughput virtual screening (HTVS) methodology can accelerate the discovery of novel energetic materials with improved properties. As a result, the newly identified and synthesized energetic molecule ICM-104 revealed excellence in performance and thermostability. Theoretical approaches are pivotal in elucidating the mechanisms underlying thermal stability, enabling the prediction and design of enhanced thermal stability for emerging EMs. These insights are instrumental in accelerating the development of novel energetic materials that optimally balance performance and thermal stability. [ABSTRACT FROM AUTHOR]

Platinum supramolecular complexes based on photosensitizers have garnered great interest in photodynamic therapy (PDT) due to Pt (II) centers as chemotherapeutic agents to eliminate tumor cells completely, which greatly improve the antitumor efficacy of PDT. However, in comparison to precursor photosensitizer ligand, the formed platinum supramolecular complexes typically exhibit inferior outcomes in terms of reactive oxygen species (ROS) generation. How to boost ROS generation in the formed platinum supramolecular complexes for enhanced PDT is an enticing yet highly challenging task. Here we report a Pt‐coordination‐based dimeric photosensitizer complex (Cz−BTZ−Py)2Pt(OTf)2. It is found that comparing with photosensitizer ligand Cz−BTZ−Py, the formed supramolecular complex exhibit redshifts of absorption wavelength as well as enhanced ROS generation efficiency. Moreover, type‐I ROS generation (O2⋅−) is produced in the formed platinum supramolecular complexes mainly due to a reduced energy gap ΔEST resulting from exciton coupling between two photosensitizer ligands. And type‐I ROS (O2⋅−) generation significantly amplifies the photodynamic therapy (PDT) outcomes. In vitro evaluation shows excellent photochemotherapy performance of (Cz−BTZ−Py)2Pt(OTf)2 nanoparticles. We anticipate this work would provide a novel approach to design type‐I photosensitizers for efficient PDT. [ABSTRACT FROM AUTHOR]

In this study, the sensing mechanism of (2E,4E)-5-(4-(dimethylamino)phenyl)-1-(2-(2,4dinitrophenoxy)phenyl)penta-2,4-dien-1-one (DAPH-DNP) towards thiophenols was investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). The DNP group plays an important role in charge transfer excitation. Due to the typical donor-excited photo-induced electron transfer (d-PET) process, DAPH-DNP has fluorescence quenching behavior. After the thiolysis reaction between DAPH-DNP and thiophenol, the hydroxyl group is released, and DAPH is generated with the reaction showing strong fluorescence. The fluorescence enhancement of DAPH is not caused by an excited-state intramolecular proton transfer (ESIPT) process. The potential energy curves (PECs) show that DAPH-keto is less stable than DAPH-enol. The frontier molecular orbitals (FMOs) of DAPH show that the excitation process is accompanied by intramolecular charger transfer (ICT), and the corresponding character of DAPH was further confirmed by hole-electron and interfragment charge transfer (IFCT) analysis methods. Above all, the sensing mechanism of the turn-on type probe DAPH-DNP towards thiophenol is based on the PET mechanism. [ABSTRACT FROM AUTHOR]

N‐protonation for numerous fluorophores is widely known as an efficient switch for the fluorescence turn‐on/off in acidic conditions, which has been applied in various scenarios that involve pH monitoring. Yet the universal mechanism for fluorescence regulation through N‐protonation is still elusive. Herein, the excited state deactivation processes are systematically investigated for a series of nitrogen‐containing fluorescent probes through theoretical approaches. Two types of mechanisms for the complex fluorescent phenomena by N‐protonation are concluded: one is through the regulation for the transition to a ππ* twisted intramolecular charge transfer (TICT) state; the other one applies for the case when nonradiative decay pathway is predominant by a dark nπ* state, which is also accompanied by an evident structural twisting and can be regarded as another kind of TICT state. More generally, the formation of the TICT state is closely related to the conjugated π‐electrons on the single bond that links the acceptor and donor part of fluorophores, which provides a simple strategy for evaluating the occurrence of the TICT process. The current contributions can bring novel insights for the rational design of functional fluorophores that involve TICT process in the excited states. [ABSTRACT FROM AUTHOR]

The photophysical properties of the Schiff base family are crucial for their applications such as molecular switches and molecular memories. However, it was found that the photophysical behavior is not uniform for all Schiff base molecules, which shows a significant substituent dependent property. In this article, we studied the photoisomerization mechanism of one Schiff base chlorosubstituted derivative 2-(1-(methylimino)methyl)-6-chlorophenol by employing geometrical optimization, energy profiles scanning, and on-the-fly dynamical simulations. Three types of minimum energy conical intersections were located on the S1/S0 crossing seam, with two characterized by twisting motion of the C=N bond and one featured with the excited state intramolecular proton transfer process and then twisting motion around the C=C bond [excited-state intramolecular proton transfer process (ESIPT)-then-twisting]. By a combination of the dynamics simulation results with the energy profiles scanned along with the ESIPT coordinate, it was found that the photophysical property of the targeted molecule is different from that of most Schiff base members, which prefer to decay by a twisting motion around the C=N bridge bond rather than the ESIPT-then-twisting channel. The minor ESIPT channel is probably governed by a tunneling mechanism. The proposed deactivation mechanism can provide a reasonable explanation for the observations in the experiment and would provide fundamental indications for further design of new and efficient photochromic products. [ABSTRACT FROM AUTHOR]

Triplet exciton‐based long‐lived phosphorescence is severely limited by the thermal quenching at high temperature. Herein, we propose a novel strategy based on the energy transfer from triplet self‐trapped excitons to Mn2+ dopants in solution‐processed perovskite CsCdCl3. It is found the Mn2+ doped hexagonal phase CsCdCl3 could simultaneously exhibit high emission efficiency (81.5 %) and long afterglow duration time (150 s). Besides, the afterglow emission exhibits anti‐thermal quenching from 300 to 400 K. In‐depth charge‐carrier dynamics studies and density functional theory (DFT) calculation provide unambiguous evidence that carrier detrapping from trap states (mainly induced by Cl vacancy) to localized emission centers ([MnCl6]4−) is responsible for the afterglow emission with anti‐thermal quenching. Enlightened by the present results, we demonstrate the application of the developed materials for optical storage and logic operation applications. [ABSTRACT FROM AUTHOR]

The level of selenocysteine (Sec) in the human body is closely related to a variety of pathophysiological states, so it is important to study its fluorescence sensing mechanism for designing efficient fluorescent probes. Herein, we used time-dependent density functional theory to investigate the fluorescence sensing mechanism of phenanthroimidazole derivates A4 and B4 for the detection of Sec, which are proposed to be designed based on excited state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT) mechanisms. The calculation results show that the fluorescence quenching mechanism of A4 and B4 is due to the photo-induced electron transfer (PET) process with the sulfonate group acts as the electron acceptor. Subsequently, A4 and B4 react with Sec, the sulfonate group is substituted by hydroxyl groups, PET is turned off, and significant fluorescence enhancement of the formed A3 and B3 is observed. The theoretical results suggest that the fluorescence enhancement mechanism of B3 is not based on ICT mechanism, and the charge transfer phenomenon was not observed by calculating the frontier molecular orbitals, and proved to be a local excitation mode. The reason for the fluorescence enhancement of A3 based on ESIPT is also explained by the calculated potential energy curves. [ABSTRACT FROM AUTHOR]

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). [ABSTRACT FROM AUTHOR]

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). [ABSTRACT FROM AUTHOR]

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-HOB<2-HSB<2-HSeB. Correspondingly, the magnitude of the energy barrier of the potential energy curve is 2-HOB>2-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. [ABSTRACT FROM AUTHOR]

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 Cs2PtxSn1−xCl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2PtxSn1−xCl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2PtxSn1−xCl6 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. [ABSTRACT FROM AUTHOR]