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Theoretical modeling of the solid-state photocatalysis is one of the important issues as various useful photocatalysts have been developed to date. In this work, we investigated the mechanism of the alcohol photooxidation on niobium oxide (Nb 2 O 5 ) which was experimentally developed, using the density functional theory (DFT)/time-dependent (TD)DFT calculations based on the cluster model. The alcohol adsorption and the first hydrogen transfer from hydroxy group to surface occur in the ground state, while the second hydrogen transfer from CH proceeds in the excited states during the photoirradiation of UV or visible light. The spin crossing was identified and the low-lying triplet states were solved for the reaction pathway. The photoabsorption in the visible light region was characterized as the charge transfer transition from O 2p of alcohol to Nb 4d of the Nb 2 O 5 surface. The spin density and the natural population analysis indicated the generation of spin density in the moiety of carbonyl compound and its dissipation to the interface of the surface, which partly explains the electron paramagnetic resonance measurement. It was confirmed that the rate determining step is the desorption of carbonyl compound and water molecule in agreement with the experimental rate equation analysis. The present findings with the theoretical modeling will provide useful information for the further studies of the solid-state photocatalysis., (© 2024 The Author(s). Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Solar cells convert light energy directly into electricity using semiconductor materials. The ternary system, composed of poly(3-hexylthiophene) (P3HT), fullerene (C 60 ), and phenyl-C 61 -butyric-acid-methyl-ester (PCBM), expressed as P3HT-C 60 -PCBM, is one of the most efficient organic solar cells. In the present study, the structures and electronic states of P3HT-C 60 -PCBM have been investigated by means of the density functional theory (DFT) method to shed light on the mechanism of charge separation in semiconductor materials. The thiophene hexamer was used as a model of P3HT. Five geometrical conformers were obtained as the C 60 -PCBM binary complexes. In the ternary system, P3HT wrapped around C 60 in the stable structure of P3HT-C 60 -PCBM. The intermolecular distances for P3HT-(C 60 -PCBM) and (P3HT-C 60 )-PCBM were 3.255 and 2.885 Å, respectively. The binding energies of P3HT + (C 60 -PCBM) and (P3HT-C 60 ) + PCBM were 27.2 and 19.1 kcal/mol, respectively. The charge transfer bands were found at the low-lying excited states of P3HT-C 60 -PCBM. These bands strongly correlated with the carrier separation and electron transfer in solar cells. The electronic states at the ground and excited states of P3HT-C 60 -PCBM were discussed on the basis of the calculated results.

Metallic nanoclusters (MNCs) were developed rapidly in recent decades, owing to their unique electronic structures and excited state characteristics, leading to their wide applications. Luminescence as one of the most important functions for MNCs has also been used to realize biodetection, displays, and lighting, through either electrochemiluminescence (ECL) or electroluminescence (EL). Both emissive properties and electrochemical activities of MNCs were utilized to enhance ECL and EL through facilitating exciton formation and radiation, rendering the rapid emerging of the latter in the last ten years. Through ligand modification, radiative excited-state components were increased to realize state-of-the-art photo- and electroluminescence efficiencies up to ∼100% and ∼30%, as well as ultralow biodetection limits. Nonetheless, material selection space and processing technologies are still limited. Herein, we overview and discuss recent advances of MNCs-based ECL and EL, through both aspects of materials/systems and devices, which would enlighten continuous innovations in optoelectronic MNCs.

Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light-induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H 2 production activity is studied using femtosecond X-ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time-dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the Fe II photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X-ray emission at the iron and cobalt K-edges in a two-color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The spin of electrons plays a vital role in chemical reactions and processes, and the excited state generated by the absorption of photons shows abundant spin-related phenomena. However, the importance of electron spin in photochemistry studies has been rarely mentioned or summarized. In this review, we briefly introduce the concept of spin photochemistry based on the spin multiplicity of the excited state, which leads to the observation of various spin-related photophysical properties and photochemical reactivities. Then, we focus on the recent advances in terms of light-induced magnetic properties, excited-state magneto-optical effects and spin-dependent photochemical reactions. The review aims to provide a comprehensive overview to utilize the spin multiplicity of the excited state in manipulating the above photophysical and photochemical processes. Finally, we discuss the existing challenges in the emerging field of spin photochemistry and future opportunities such as smart magnetic materials, optical information technology and spin-enhanced photocatalysis., (© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Imine reduction is a useful reaction in the preparation of amine derivatives. Various catalysts have been reported to promote this reaction and photoredox catalysts are promising candidates for sustainable amine synthesis. Improvement of this reaction using biomolecule-based reaction scaffolds is expected to increase the utility of the reaction. In this context, we have recently investigated photoredox Ru complexes with pentapeptide scaffolds via coordination bonds as catalysts for photoreduction of dihydroisoquinoline derivatives. First, Ru bipyridine terpyridine complexes coordinated with five different pentapeptides (XVHVV: X = V, F, W, Y, C) were prepared and characterized by mass spectrometry. Catalytic activities of the Ru complexes with XVHVV were evaluated for photoreduction of dihydroisoquinoline derivatives in the presence of ascorbate and thiol compounds as sacrificial reagents and hydrogen sources. Interestingly, the turnover number of the Ru complex with VVHVV is 531, which is two-fold higher than that of a simple Ru complex with an imidazole ligand. The detailed emission lifetime measurements indicate that the enhanced catalytic activity provided by the peptide scaffold is caused by an efficient reaction with the thiol derivative to accelerate reductive quenching of Ru complex. The quenching behavior suggests formation of an active species such as a Ru(I) complex. These findings reveal that the simple pentapeptide serves as an effective scaffold to enhance the photocatalytic activity of a photoactive Ru complex., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Inc.)

Photocytotoxicity represents a significant limitation in the application of dye-assisted fluorescence imaging (FI), often resulting in undesirable cellular damage or even cell death, thereby restricting their practical utility. The prevalence of Rhodamine B (RhB) in FI underscores the importance of elucidating its photocytotoxicity effects to minimize photodamage. This study identifies the primary cause of photocytotoxicity stems from the generation of cytotoxic singlet oxygen in RhB, utilizing femtosecond transient absorption spectroscopy coupled with quantum chemical calculations. The Laser power-dependent cellular viability reveals a threshold at about 50 mW cm -2 , surpassing which produces pronounced photocytotoxicity in vitro and in vivo. Notably, this threshold significantly falls below the safety limits (<200 mW cm -2 ) for laser use in health care, implying a huge risk of photodamage. This study provides valuable insights into the photocytotoxicity and offers essential guidelines for developing safer imaging protocols., (© 2024 Wiley‐VCH GmbH.)

Recent advances in synthetic methods, combined with tip-induced on-surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C 16 and C 18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron-withdrawing ability of cyclocarbon molecules. The vdW complexes of C 16 and C 18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from the donor partner to the cyclocarbons that occurs on a picosecond time scale. The lower reorganization energy of C 16 compared to C 18 leads to a significant acceleration of the ET reactions., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The photophysical properties of a series of recently synthesized single benzene fluorophores were investigated using ensemble density functional theory calculations. The energetic stability of the ground and excited state species were counterposed against the aromaticity index derived from local vibrational modes. It was found that the large Stokes shift of the fluorophores (up to ca. 5800 cm   - 1 ) originates from the effect of electron donating and electron withdrawing substituents rather than π -delocalization and related (anti-)aromaticity. On the basis of nonadiabatic molecular dynamics simulations, the absence of fluorescence from one of the regioisomers was explained by the occurrence of easily accessible S   1 /S   0 conical intersections below the vertical excitation energy level. It is demonstrated in the manuscript that the analysis of local mode force constants and the related aromaticity index represent a useful tool for the characterization of π -delocalization effects in π -conjugated compounds., (© 2024 Wiley Periodicals LLC.)

Monobenzopentalenes have received moderate attention compared to dibenzopentalenes, yet their accessibility as stable, non-symmetric structures with diverse substituents could be interesting for materials applications, including molecular photonics. Recently, monobenzopentalene was considered computationally as a potential chromophore for singlet fission (SF) photovoltaics. To advance this compound class towards photonics applications, the excited state energetics must be characterized, computationally and experimentally. In this report we synthesized a series of stable substituted monobenzopentalenes and provided the first experimental exploration of their photophysical properties. Structural and opto-electronic characterization revealed that all derivatives showed 1 H NMR shifts in the olefinic region, bond length alternation in the pentalene unit, low-intensity absorptions reflecting the ground-state antiaromatic character and in turn the symmetry forbidden HOMO-to-LUMO transitions of ~2 eV and redox amphotericity. This was also supported by computed aromaticity indices (NICS, ACID, HOMA). Accordingly, substituents did not affect the fulfilment of the energetic criterion of SF, as the computed excited-state energy levels satisfied the required E(S 1 )/E(T 1 )>2 relationship. Further spectroscopic measurements revealed a concentration dependent quenching of the excited state and population of the S 2 state on the nanosecond timescale, providing initial evidence for unusual photophysics and an alternative entry point for singlet fission with monobenzopentalenes., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Time-dependent density functional theory (TD-DFT) and multiconfigurational second-order perturbation theory (CASPT2) are two of the most widely used methods to investigate photoinduced dynamics in DNA-based systems. These methods sometimes give diverse dynamics in physiological environments usually modeled by quantum mechanics/molecular mechanics (QM/MM) protocol. In this work, we demonstrate for the uridine test case that the underlying topology of the potential energy surfaces of electronic states involved in photoinduced relaxation is similar in both electronic structure methods. This is verified by analyzing surface-hopping dynamics performed at the QM/MM level on aqueous solvated uridine at TD-DFT and CASPT2 levels. By constraining the dynamics to remain on π π * state we observe similar fluctuations in energy and relaxation lifetimes in surface-hopping dynamics in both TD-DFT and experimentally validated CASPT2 methods. This finding calls for a systematic comparison of the ES potential energy surfaces of DNA and RNA nucleosides at the single- and multi-reference levels of theory. The anomalous long excited state lifetime at the TD-DFT level is explained by n π * trapping due to the tendency of TD-DFT in QM/MM schemes with electrostatic embedding to underestimate the energy of the π π * state leading to a wrong π π * / n π * energetic order. A study of the FC energetics suggests that improving the description of the surrounding environment through polarizable embedding or by the expansion of QM layer with hydrogen-bonded waters helps restore the correct state order at TD-DFT level. Thus by combining TDDFT with an accurate modeling of the environment, TD-DFT is positioned as the standout protocol to model photoinduced dynamics in DNA-based aggregates and multimers., (© 2024 American Society for Photobiology.)

Photocatalytic CO 2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine-bipyridine (bpy)-phosphine (PNNP)-type Ir(III) photocatalyst, Mes-IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal-to-ligand charge transfer ( 3 MLCT) state. Subsequently, the divergence happens from the 3 MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one-electron-reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free-energy barrier in the reaction-limiting step and the very efficient SET in 3 MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO 2 reduction reaction of similar function-integrated molecular photocatalyst., (© 2023 Wiley-VCH GmbH.)

Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl-maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non-bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A series of reported Pt(II) carbene complexes possibly have the ability to serve as the new generation of blue emitters in luminescent devices because of their narrow emission spectra, high photoluminescence quantum yields (PLQYs), and rigid molecular skeleton. However, the combination of all carbene ligands with different multidentate structures will affect the overall planarity and horizontal dipole ratio to varying degrees, but the specific extent of this effect has not previously been analyzed in detail. In this work, density functional computation is used to study a class of platinum tetracarbene bidentate complexes with similar absorption and emission band characteristics, which is the main reason for the remarkable difference in quantum efficiency due to subtle differences in electronic states caused by different ligands. From the calculation results, the major reason, which results in significantly decrease in quantum efficiency for [Pt(cyim) 2 ] 2+ , is that [Pt(cyim) 2 ] 2+ can reach the non-radiative deactivation metal-centered d-d excited state through an easier pathway compared with [Pt(meim) 2 ] 2+ . The result, based on changes in the dihedral angle between ligands, can achieve the goal of improving and designing materials by adjusting the degree of the dihedral angle. (meim: bis(1,1'-dimethyl-3,3'-methylene-diimidazoline-2,2'-diylidene); cyim: bis(1,1'-dicyclohexyl-3,3'-methylene-diimidazoline-2,2'-diylidene).

We here disclose that the incorporation of thiophene rings into a seven-membered 8π azepine in a fused fashion produces a useful antiaromatic core for near-infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno-fused derivatives with electron-accepting groups adopt flat conformations in the ground state. The dithieno-fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red-shifted relative to those of the dibenzo-fused congeners. Theoretical study revealed two contradictory effects of the less-aromatic thiophene-fused structure, i.e., the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron-accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution., (© 2023 Wiley-VCH GmbH.)

Boron compound BOMes 2 containing an internal B-O bond undergoes highly efficient photoisomerization, followed by sequential structural transformations, resulting in a rare eight-membered B, O-heterocycle (S. Wang, et al. Org. Lett. 2019, 21, 5285-5289). In this work, the detailed reaction mechanisms of such a unique carbonyl-supported tetracoordinate boron system in the first excited singlet (S 1 ) state and the ground (S 0 ) state were investigated by using the complete active space self-consistent field and its second-order perturbation (MS-CASPT2//CASSCF) method combined with time-dependent density functional theory (TD-DFT). Moreover, an imine-substituted tetracoordinated organic boron system (BNMes 2 ) was selected for comparative study to explore the intrinsic reasons for the difference in reactivity between the two types of compounds. Steric factor was found to influence the photoisomerization activity of BNMes 2 and BOMes 2 . These results rationalize the experimental observations and can provide helpful insights into understanding the excited-state dynamics of heteroatom-doped tetracoordinate organoboron compounds, which facilitates the rational design of boron-based materials with superior photoresponsive performances., (© 2023 Wiley-VCH GmbH.)

Disulfide bonds are critical structural elements in proteins and stabilize folded structures. Modification of these linkages is associated with a loss of structure and function. Previous studies have reported large variations in the rate of disulfide oxidation by hypohalous acids, due to stabilization of reaction intermediates. In this study we hypothesized that considerable variation (and hence selective oxidation) would occur with singlet oxygen ( 1 O 2 ), a key intermediate in photo-oxidation reactions. The kinetics of disulfide-mediated 1 O 2 removal were monitored using the time-resolved 1270 nm phosphorescence of 1 O 2 . Stern-Volmer plots of these data showed a large variation (∼10 3 ) in the quenching rate constants k q (from 2 × 10 7 for α-lipoic acid to 3.6 × 10 4  M -1 s -1 for cystamine). The time course of disulfide loss and product formation (determined by LC-MS) support a role for 1 O 2 , with mono- and di-oxygenated products detected. Elevated levels of these latter species were generated in D 2 O- compared to H 2 O buffers, which is consistent with solvent effects on the 1 O 2 lifetime. These data are interpreted in terms of the intermediacy of a zwitterion [-S + (OO - )-S-], which either isomerizes to a thiosulfonate [-S(O) 2 -S-] or reacts with another parent molecule to give two thiosulfinates [-S(O)-S-]. The variation in quenching rates and product formation are ascribed to zwitterion stabilization by neighboring, or remote, lone pairs of electrons. These data suggest that some disulfides, including some present within or attached to proteins (e.g., α-lipoic acid), may be selectively modified, and undergo subsequent cleavage, with adverse effects on protein structure and function., Competing Interests: Declaration of competing interest MJD declares consultancy contracts with Novo Nordisk A/S. This funder had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results. The other authors declare no conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Photo-controlled self-assembly of nanoparticles (NPs) is an advanced and promising approach to address a series of material issues from the molecular level to the nano/micro scale, owing to the fact that light stimulus is typically precise and rapid, and can provide contactless spatial and temporal control. The traditional photo-controlled assembly of NPs is based on photochemical processes through NPs modified by photo-responsive molecules, which are realized through the change in chemical structure under irradiation. Moreover, photoexcitation-induced assembly of NPs is another promising physical strategy, and such a strategy aims to employ molecular conformational change in the excited state (rather than the chemical structure) to drive molecular motion and assembly. The exploration and control of NP assembly through such a photo-controlled strategy can open a new paradigm for scientists to deal with "bottom-up" behaviors and develop unprecedented optoelectronic functional materials.

Fluoropurine analogues are a kind of unnatural bases, which are widely used in chemistry, biological science, pharmacy and other fields. At the same time, fluoropurine analogues of aza-heterocycles play an important role in medicinals research and development. In this work, the excited state behavior of a group of newly developed fluoropurine analogues of aza-heterocycles, triazole pyrimidinyl fluorophores, was comprehensively studied. The reaction energy profiles indicate that excited state intramolecular proton transfer (ESIPT) is difficult to happen, which is further proved by fluorescent spectra results. This work proposed a new and reasonable fluorescence mechanism based on the original experiment, and found that the large Stokes shift of the triazole pyrimidine fluorophore is due to the intramolecular charge transfer (ICT) process of the excited state. Our new discovery is of great significance for the application of this group of fluorescent compounds in other fields and the regulation of fluorescence properties., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Vacuum ultraviolet (VUV) based advanced oxidation processes (AOPs) recently attracted widespread interests. However, the role of UV 185 in VUV is only considered to be generating a series of active species, while the effect of photoexcitation has long been overlooked. In this work, the role of UV 185 induced high-energy excited state for the dephosphorization of organophosphorus pesticides was studied using malathion as a model. Results showed malathion degradation was highly related to radical yield, while its dephosphorization was not. It was UV 185 rather than UV 254 or radical yield that was responsible for malathion dephosphorization by VUV/persulfate. DFT calculation results demonstrated that the polarity of P-S bond was further increased during UV 185 excitation, favoring dephosphorization while UV 254 did not. The conclusion was further supported by degradation path identification. Moreover, despite the fact that anions (Cl - , SO 4 2 - and NO 3 - ) considerably affected radical yield, only Cl - and NO 3 - with high molar extinction coefficient at 185 nm significantly affected dephosphorization. This study shed light on the crucial role of excited states in VUV based AOPs and provided a new idea for the development of mineralization technology of organophosphorus pesticides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Carbon nanodots (CNDs) synthesized from citric acid and formyl derivatives, that is, formamide, urea, or N-methylformamide, stand out through their broad-range visible-light absorbance and extraordinary photostability. Despite their potential, their use has thus far been limited to imaging research. This work has now investigated the link between CNDs' photochemical properties and their chemical structure. Electron-rich, yellow carbon nanodots (yCNDs) are obtained with in situ addition of NaOH during the synthesis, whereas otherwise electron-poor, red carbon nanodots (rCNDs) are obtained. These properties originate from the reduced and oxidized dimer of citrazinic acid within the matrix of yCNDs and rCNDs, respectively. Remarkably, yCNDs deposited on TiO 2 give a 30% higher photocurrent density of 0.7 mA cm -2 at +0.3 V versus Ag/AgCl under Xe-lamp irradiation (450 nm long-pass filter, 100 mW cm -2 ) than rCNDs. The difference in overall photoelectric performance is due to fundamentally different charge-transfer mechanisms. These depend on either the electron-accepting or the electron-donating nature of the CNDs, as is evident from photoelectrochemical tests with TiO 2 and NiO and time-resolved spectroscopic measurements., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

The photo-responsive adsorption has emerged as a vibrant area, but its current methodology is limited by the well-defined photochromic units and their molecular deformation driven by photo-stimuli. Herein, a methodology of nondeforming photo-responsiveness is successfully exploited. With the exploiting agent of Cu-TCPP framework assembled on the graphite and strongly interacted with it, the sorbent generates two kinds of adsorption sites, over which the electron density distribution of the graphite layer can be modulated at the c-axis direction, which can further evolve due to photo-stimulated excited states. The excited states are stable enough to meet the timescale of microscopic adsorption equilibrium. Independent of the ultra-low specific surface area of the sorbent (20 m 2  g -1 ), the CO adsorption capability can be improved from 0.50 mmol g -1 at the ground state to 1.24 mmol g -1 (0 °C, 1 bar) with the visible light radiation, rather than the photothermal desorption., (© 2023 Wiley-VCH GmbH.)

Developing organic photothermal materials (OPMs) with high photothermal performance for phototheranostic mainly focus on the manipulation of intramolecular nonradiative (intraNR) decay, which often requires quite complicated and time-consuming molecular engineering. In addition to intraNR decay, intermolecular nonradiative (interNR) decay is equally important and more convenient in governing photothermal performance. However, controlling interNR decay remains challenging due to the limited understanding of their origin and dynamics. Here, systemic investigation of intraNR and interNR decay directs the first demonstration of simple manipulation of interNR decay to produce a giant photothermal performance for optimized phototheranostic. Among three designed polymers with varying fluorine substitution, structure-performance studies reveal a dimer-initiated interNR decay to improve photothermal performance. Dimer is formed by intermolecular CF···H hydrogen bond. This finding inspires a simple aggregation control strategy to form excited dimer, namely, excimer. It initiates an ≈100-fold enhancement in interNR decay rate over conventional intraNR decay to produce ultrahigh photothermal conversion efficiency of 81% for efficient photoacoustic imaging-guided photothermal therapy in vivo. This study provides insights into interNR decay in achieving a giant photothermal effect and paves a convenient way to develop high-performance OPMs., (© 2023 Wiley-VCH GmbH.)

Donor-π-acceptor fluorophores that consist of an electron-donating amino group and an electron-accepting triarylborane moiety generally exhibit substantial solvatochromism in their fluorescence while retaining high fluorescence quantum yields even in polar media. Herein, we report a new family of this compound class, which bears ortho-P(=X)R 2 -substituted phenyl groups (X=O or S) as a photodissociative module. The P=X moiety that intramolecularly coordinates to the boron atom undergoes dissociation in the excited state, giving rise to dual emission from the corresponding tetra- and tricoordinate boron species. The susceptibility of the systems to photodissociation depends on the coordination ability of the P=O and P=S moieties, whereby the latter facilitates dissociation. The intensity ratios of the dual emission bands are sensitive to environmental parameters, including temperature, solution polarity, and the viscosity of the medium. Moreover, precise tuning of the P(=X)R 2 group and the electron-donating amino moiety led to single-molecule white emission in solution., (© 2023 Wiley-VCH GmbH.)

Helicenes are an interesting scaffold for chiroptical properties and in particular circularly polarized luminescence (CPL). In this short review, we collect the luminescence (g lum ) and absorption (g abs ) dissymmetry factors associated to the first Cotton effect of the electronic circular dichroism (ECD) spectrum. Considering the data for 170 [n]-helicenes (n = 4-11), overall we found reasonable correlations between g lum and g abs . Despite a few notable exceptions, this would confirm a similarity in the stereochemistry of the ground and emitting excited states for most helicenes. These results may be useful in rationalizing chiroptical data and help chemists in designing new helicene structures with the desired CPL properties., (© 2023 The Authors. Chirality published by Wiley Periodicals LLC.)

Pressure-induced emission (PIE) associated with self-trapping excitons (STEs) in low-dimensional halide perovskites has attracted great attention for better materials-by-design. Here, using 2D layered double perovskite (C 6 H 5 CH 2 CH 2 NH 3 + ) 4 AgBiBr 8 as a model system, we advance a fundamental physicochemical mechanism of the PIE from the perspective of carrier dynamics and excited-state behaviors of local lattice distortion. We observed a pressure-driven STE transformation from dark to bright states, corresponding a strong broadband Stokes-shifted emission. Further theoretical analysis demonstrated that the suppressed lattice distortion and enhanced electronic dimensionality in the excited-state play an important role in the formation of stabilized bright STEs, which could manipulate the self-trapping energy and lattice deformation energy to form an energy barrier between the potential energy curves of ground- and excited-state, and enhance the electron-hole orbital overlap, respectively., (© 2023 Wiley-VCH GmbH.)

In this review, we have attempted to briefly summarize the influence of an external electric field on an assembly of tautomeric molecules and to what experimentally observable effects this interaction can lead to. We have focused more extensively on the influence of an oriented external electric field (OEEF) on excited-state intramolecular proton transfer (ESIPT) from the studies available to date. The possibilities provided by OEEF for regulating several processes and studying physicochemical processes in tautomers have turned this direction into an attractive area of research due to its numerous applications.