Regulating Planarized Intramolecular Charge Transfer for Efficient Single-Phase White-Light Emission in Undoped Metal-Organic Framework Nanocrystals.

The technology of combining multiple emission centers to exploit white-light-emitting (WLE) materials by taking advantage of porous metal-organic frameworks (MOFs) is mature, but preparing undoped WLE MOFs remains a challenge. Herein, a pressure-treated strategy is reported to achieve efficient white photoluminescence (PL) in undoped [Zn(Tdc)(py)]n nanocrystals (NCs) at ambient conditions, where the Commission International del'Eclairage coordinates and color temperature reach (0.31, 0.37) and 6560 K, respectively. The initial [Zn(Tdc)(py)]n NCs exhibit weak-blue PL consisting of localized excited (LE) and planarized intramolecular charge transfer (PLICT) states. After pressure treatment, the emission contributions of LE and PLICT states are balanced by increasing the planarization of subunits, thereby producing white PL. Meanwhile, the reduction of nonradiative decay triggered by the planarized structure results in 5-fold PL enhancement. Phosphor-converted light-emitting diodes based on pressure-treated samples show favorable white-light characteristics. The finding provides a new platform for the development of undoped WLE MOFs.

Lipid Droplets Specific Fluorophore for Demarcation of Normal and Diseased Tissues.

Using high-fidelity, permeable, lipophilic, and bright fluorophores for imaging lipid droplets (LDs) in tissues holds immense potential in diagnosing conditions such as diabetic or alcoholic fatty liver disease. In this work, we utilized linear and Λ-shaped polarity-sensitive fluorescent probes for imaging LDs in both cellular and tissue environments, specifically in rats with diabetic and alcoholic fatty liver disease. The fluorescent probes possess several key characteristics, including high permeability, lipophilicity, and brightness, which make them well-suited for efficient LD imaging. Notably, the probes exhibit a substantial Stokes shift, with 143 nm for DCS and 201 nm for DCN with selective targeting of the lipid droplets. Our experimental investigations successfully differentiated morphological variations between diseased and normal tissues in three distinct tissue types: liver, adipose, and small intestine. They could help provide pointers for improved detection and understanding of LD-related pathologies.

Photophysical Analysis of Aggregation-Induced Emission (AIE) Luminogens Based on Triphenylamine and Thiophene: Insights into Emission Behavior in Solution and PMMA Films.

Aggregation-Induced Emission (AIE) luminogens have garnered significant interest due to their distinctive applications in different applications. Among the diverse molecular architectures, those based on triphenylamine and thiophene hold prominence. However, a comprehensive understanding of the deactivation mechanism both in solution and films remains lacking. In this study, we synthesized and characterized spectroscopically two AIE luminogens: 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carbaldehyde (TTY) and 5'-(4-(bis(4-methoxyphenyl)amino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde (TTO). Photophysical and theoretical analyses were conducted in both solution and PMMA films to understand the deactivation mechanism of TTY and TTO. In diluted solutions, the emission behavior of TTY and TTO is influenced by the solvent, and the deactivation of the excited state can occur via locally excited (LE) or twisted intramolecular charge transfer (TICT) state. In PMMA films, rotational and translational movements are constrained, necessitating emission solely from the LE state. Nevertheless, in the PMMA film, excimers-like structures form, resulting in the emergence of a longer wavelength band and a reduction in emission intensity. The zenith of emission intensity occurs when molecules are dispersed at higher concentrations within PMMA, effectively diminishing the likelihood of excimer-like formations. Luminescent Solar Concentrators (LSC) were fabricated to validate these findings, and the optical efficiency was studied at varying concentrations of luminogen and PMMA.

Unveiling the Twisted Aromatic Donor Effect on the Nonlinear Response of D-π-A Type Malononitrile-Derived Chromophores.

This study presents the design, synthesis, and comprehensive characterization of a novel series of D-π-A type malononitrile-derived chromophores, BTC-1 to BTC-4. Combining various spectroscopic techniques, nonlinear Z-scan measurements, and quantum chemical calculations, we revealed the intricate relationship between nonlinear optical properties and the interplay of molecular structure, intramolecular charge transfer (ICT), and dipole moments (µ). Our experimental and computational findings corroborate that the polarization degree in the ground state, the charge separation in the excited state and ICT collectively dictate the nonlinear optical properties of the compounds. Notably, BTC-1 exhibits an exceptional nonlinear absorption coefficient ß value (2 × 10-8 m W-1), attributed to its optimized charge transfer efficiency and pronounced degree of charge separation. Our findings provide actionable insights for the rational design of high-performance organic NLO materials with potential applications in advanced photonic devices.

Design of 2-Pyridone Fluorophores for Brighter Emissions at Longer Wavelengths.

The recent discovery of blue fluorophores with high quantum yields based on pyridone structures inspired the development of new low-molecular-weight fluorophores with bright emissions at tunable wavelengths, which are highly attractive for various applications. In this study, we propose a rational design strategy for 2-pyridone-based fluorophores with bright emissions at long wavelengths. With a detailed understanding of the positional substitution effects on each carbon atom of the 2-pyridone core, we developed a bright blue fluorophore (λabs =377 nm; λem =433 nm; ϵ=13,200 M-1 cm-1 ; ϕF =88 %) through C3 -aryl and C4 -ester substitutions followed by cyclization. Furthermore, by applying the intramolecular charge transfer (ICT) principle, we invented a bright green fluorophore through C3 - and C4 -diester and C6 -aryl substitutions. The ICT fluorophore based on the pyridone structure shows large molar absorptivity (ϵ=20,100 M-1 cm-1 ), longer emission wavelength (λem =539 nm), high emission quantum yield (ϕF =74 %), and large Stokes shift (Δv=5720 cm-1 ), which are comparable to those of practical fluorescent probes.

Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

Highly and Deep Red-luminescent Bisphenylamine-appended Benzocarcogendiazole Fluorophores.

Benzocarcogendiazole units have been frequently utilized for optoelectronics such as organic solar cells because of their robustness, rigidity, and band-gap tunability based on the strong electron-withdrawing properties. Focusing on the luminescent characteristics, these molecules have been utilized to demonstrate highly sensitive chromisms because of the potential of charge transfer. Here, we demonstrate deep red-emissions in bis(4-tert-butylphenyl)amine-appended benzocarcogendiazole-based donor-acceptor-donor (D-A-D) fluorophores, namely 1 and 2. Because benzocarcogendiazole and bis(4-tert-butylphenyl)amineserve as strong electron acceptor and donor, respectively, strong intramolecular charge transfer (ICT) enables long wavelength of photoluminescence (PL) even in the small molecular weight. Although photoluminescence (PL) in long wavelength tends to exhibit quite low PL quantum efficiency (ΦPL), the values of solutions 1 and 2 are quite high (up to 50 %). According to X-ray crystallographic characterizations and DFT calculations, these high ΦPL values are attributable to the segregated π-planes of benzocarcogendiazole units, which is induced by the bulky substituents of bis(4-tert-butylphenyl)amines.

Inherent D-A Architecture in Indoloquinoxalines with an Array of Substituents for Non-Volatile Memory Device Applications.

Donor-acceptor (D-A)-based architecture has been the key to increase storage capability efficiency through the enhanced charge transportation in the fabricated device. We have designed and synthesized a series of functionalized indoloquinoxalines (IQ) for non-volatile organic memory devices. The investigation on UV-visible spectra reveals the absorption maxima of the compounds around 420 nm, attributed to the intramolecular charge transfer between indole and quinoxaline moiety. The irreversible anodic peak in the 1.0 to 1.5 V range indicates the indole moiety's oxidation ability. Besides, the cathodic peak in the range of -0.5 to -1.0 V, contributed to the stability of the reduced quinoxaline unit. All the compounds exhibited uniformly covered thin film in SEM analysis, potentially facilitating the seamless charge carrier migration between adjacent molecules. The methoxyphenyl substituted compound exhibited the binary write-once read-many (WORM) memory behavior with the lowest threshold voltage of -0.81 V. The molecular simulations displayed the efficient intramolecular charge transfer, providing the fabricated device's distinctive conductive states. Except for the tert-butylphenyl compound, which showed volatile dynamic random-access memory (DRAM) behavior, all the other compounds exhibited non-volatile WORM memory behavior, suggesting IQs potential as an intrinsic D-A molecule in organic memory devices on further structural refinement.

Fluorescent Probes Based on Charge and Proton Transfer for Probing Biomolecular Environment.

Fluorescent probes for sensing fundamental properties of biomolecular environment, such as polarity and hydration, help to study assembly of lipids into biomembranes, sensing interactions of biomolecules and imaging physiological state of the cells. Here, we summarize major efforts in the development of probes based on two photophysical mechanisms: (i) an excited-state intramolecular charge transfer (ICT), which is represented by fluorescent solvatochromic dyes that shift their emission band maximum as a function of environment polarity and hydration; (ii) excited-state intramolecular proton transfer (ESIPT), with particular focus on 5-membered cyclic systems, represented by 3-hydroxyflavones, because they exhibit dual emission sensitive to the environment. For both ICT and ESIPT dyes, the design of the probes and their biological applications are summarized. Thus, dyes bearing amphiphilic anchors target lipid membranes and report their lipid organization, while targeting ligands direct them to specific organelles for sensing their local environment. The labels, amino acid and nucleic acid analogues inserted into biomolecules enable monitoring their interactions with membranes, proteins and nucleic acids. While ICT probes are relatively simple and robust environment-sensitive probes, ESIPT probes feature high information content due their dual emission. They constitute a powerful toolbox for addressing multitude of biological questions.

Oxidized Bisindolyl-Based Amphiphilic Probe for Dual Mode Analysis of Heavy Metal Pollutants in Aqueous Medium.

The oxidized bisindolyl-based amphiphilic, chromogenic probe has been synthesized that can form nanoscopic aggregates in the aqueous medium. Along with solvent polarity and pH of the medium, it was observed that the addition of heavy metal pollutants, like Hg2+ can cause significant alteration in the charge transfer state. This resulted in the immediate change in the solution color from yellow to orange. Additionally, we could excite either the monomer species or the aggregates of the probe by choosing the proper excitation wavelength. Upon exciting at 390 nm, the compound exhibited a broad fluorescence spectrum with maxima at 450 nm, presumably due to twisted state charge transfer. On the contrary, the aggregated species (λex = 465 nm) displayed a comparatively weaker fluorescence band centered at 565 nm. Interestingly, the fluorescence intensity at the 450 nm band experience fluorescence quenching in the presence of Hg2+ ion, while the aggregate emission band remained unaffected. Finally, the present system was utilized for detection of mercury ions in natural water samples.

Synthesis and Photophysical Properties of Bipolar Compound: Triphenylamine/Diazafluorene-Carbazole.

Carbazole and triphenylamine, are two well-known hole transporting units that are attached to electron transporting unit 4,5-diazafluorene in a fascinating way to bring out non-planar configuration of a molecule. The synthesized compound exhibits good thermal stability (Td > 515 °C) and high glass transition temperature (Tg, 191 °C). Optical bandgap (Egopt) obtained from solid state absorption spectra was calculated to be 2.93 eV. Solid state photoluminescence spectra displays the emission maxima at 473 nm. The emission characteristics of the compound observed in solvents of different polarity confirms the existence of intramolecular charge transfer in their excited state. Density functional theory studies reveal that HOMO and HOMO-1 localized on triphenylamine is spatially separated from LUMO of 4,5-diazafluorene, which manifest its bipolar character. The realization of long lived charge separated state upon photo-excitation from time resolved photoluminescence studies ascertains the charge transfer from triphenylamine to 4,5-diazafluorene. The experimental and theoretical analysis of the compound proved it to be a promising candidate for the fabrication of OLED devices.

α-Cyanostilbene-based Molecule with the Synergistical Mechanisms of AIE, ESIPT and TICT: A New Schiff Base Probe for Selective Detection of Fe3+ and Reversible Response to HCl/NH3 Vapor.

We designed and synthesized a new Schiff base probe, which incorporated the salicylaldehyde-analogue α-cyanostilbene and benzophenone hydrazone by the imine linkage. Its chemical structure was verified by FT-IR, MALDI-TOF-MS, HR-MS and 1H/13C NMR technologies. It could exhibit a red fluorescence based on the synergistical effects of aggregation-induce emission (AIE), excited-state intramolecular proton transfer (ESIPT) and twisted intramolecular charge-transfer (TICT) in the aggregation or solid states. Interestingly, the TLC-based test strip loaded with the target compound showed the reversible fluorescence response to amine/acid vapor and on-site visual fluorescence quenching response to Fe3+. In THF/water mixtures (fw = 90%, 10 µM, pH = 7.4), the detection limit (DL) and the binding constant (Ka) of the developed probe towards Fe3+ were evaluated as 5.50 × 10- 8 M and 1.69 × 105, respectively. The developed probe was successfully applied for the detection of Fe3+ with practical, reliable, and satisfying results.

Ultrabright Acrylic Polymers with Tunable Fluorescence Enabled by Imprisoning Single TICT Probe.

Bright and colorful fluorescent polymers are ideal materials for a variety of applications. Although polymers could be made fluorescent by physical doping or chemical binding of fluorescent units, it is a great challenge to get colorful and highly emissive polymers with a single fluorophore. Here the development of a general and facile method to synthesize ultrabright and colorful polymers using a single twisted intramolecular charge transfer (TICT) probe is reported. By incorporating polymerizable, highly fluorescent, and environmental sensitive TICT probe, a series of colorful acrylic polymers (emission from 481 to 543 nm) with almost 100% fluorescence quantum yields are prepared. Like the solvatochromic effect, functional groups within side chains of acrylic polymers (including alkyl chain, tetrahydrofurfuryl group, and hydroxyl group) provide varied environmental polarity for the incorporated fluorophore, resulting in a series of colorful polymeric materials. Benefiting from the excellent photophysical properties, the polymers show great potential in encryption, cultural relics protection, white light-emitting diode bulb making, and fingerprint identification.

Cooperativity of ESPT and Aggregation-Induced Emission Effects-An Experimental and Theoretical Analysis of a 1,3,4-Thiadiazole Derivative.

4-[5-(Naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol (NTBD) was extensively studied through stationary UV-vis absorption and fluorescence measurements in various solvents and solvent mixtures and by first-principles quantum chemical calculations. It was observed that while in polar solvents (e.g., methanol) only a single emission band emerged; the analyzed 1,3,4-thiadiazole derivative was capable of producing dual fluorescence signals in low polarity solvents (e.g., n-hexane) and certain solvent mixtures (e.g., methanol/water). As clearly follows from the experimental spectroscopic studies and theoretical modeling, the specific emission characteristic of NTBD is triggered by the effect of enol → keto excited-state intramolecular proton transfer (ESIPT) that in the case of solvent mixture is reinforced by aggregation of thiadiazole molecules. Specifically, the restriction of intramolecular rotation (RIR) due to environmental hindrance suppresses the formation of non-emissive twisted intramolecular charge transfer (TICT) excited keto* states. As a result, this particular thiadiazole derivative is capable of simultaneously producing both ESIPT and aggregation-induced emission (AIE).

Screening the Optimal Probe by Expounding the ESIPT Mechanism and Photophysical Properties in Bis-HBX with Multimodal Substitutions.

DFT and TD-DFT were used in this article to investigate the effects of different substitutions at multiple sites on the photophysical mechanism of bis-HBX in the gas phase. Four different substitution modes were selected, denoted as A1 (X=Me, Y=S), A2 (X=OMe, Y=S), B1 (X=Me, Y=NH), and C1 (X=Me, Y=O). The geometric parameters proved that the IHBs enhanced after photoexcitation, which was conducive to promote the ESIPT process. Combining the analysis of the PECs, it was revealed that the bis-HBX molecule underwent the ESIPT process, and the ease of the ESIPT process was in the order of A1 > A2> B1 > C1. In particular, the TICT process in A1 and B1 promoted the occurrence of the ESIPT process. In addition, the IC process was identified, particularly in C1. Meanwhile, the calculation of fluorescence lifetime and fluorescence rate further confirmed that A1 was the most effective fluorescent probe molecule. This theoretical research provides an innovative theoretical reference for regulating ESIPT reactions and optimizing fluorescent probe molecules.

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.

Coherent Modulation of the Aggregation Behavior and Intramolecular Charge Transfer in Small Molecule Probes for Sensitive and Long-term Nerve Agent Monitoring.

Aggregation-induced emission (AIE) shows promising performance in chemical sensing relying on the change of the emission behavior of the probe molecule monomers to the aggregated product. However, whether the response contrast could be further boosted by utilizing the emission property of the aggregated probe and the aggregated product remains a big challenge. Here, an exciting AIE probe regulation strategy was proposed by coherently modulating the aggregation behavior and the intramolecular charge transfer (ICT) property of the probes and thus an aggregated-to-aggregated colorimetric-fluorescent dual-mode detection was achieved. The blue emissive film obtained with the optimal AIE probe has been proven to be effective to recognize the vapor of nerve agent analog DCP in air by emitting a sharp green fluorescence. In addition, a porous polymer-based wet sensing chip loaded with the probe enables the immediate response to DCP vapor with a limit of detection (LOD) of 1.7 ppb, and it was further integrated into a wearable watch device for long-term monitoring of DCP vapor up to two weeks. We expect the present probe design strategy would greatly deepen the AIE-based science and provide new insights for long-term monitoring sensors toward trace hazardous substances.

Near-Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy.

Near-infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen (1O2) generation ability, indicated by low 1O2 quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S (Scy7) and Se (Secy7) atom. We observe that Secy7 exhibits a redshift in the main absorption to ~840 nm and an ultra-efficient 1O2 generation capacity. The emergence of a strong intramolecular charge transfer effect between the Se atom and polymethine chain considerably narrows the energy gap (0.51 eV), and the heavy atom effect of Se strengthens spin-orbit coupling (1.44 cm-1), both of which greatly improved the high triplet state yield (61%), a state that determines the energy transfer to O2. Therefore, Secy7 demonstrated excellent 1O2 generation capacity, which is ~24.5-fold that of indocyanine green, ~8.2-fold that of IR780, and ~1.3-fold that of methylene blue under low-power-density 850 nm irradiation (5 mW cm-2). Secy7 exhibits considerable phototoxicity toward cancer cells buried under 12 mm of tissue. Nanoparticles formed by encapsulating Secy7 within amphiphilic polymers and lecithin, demonstrated promising antitumor and anti-pulmonary metastatic effects, exhibiting remarkable potential for advancing PDT in deep tissues.

Perspectives on push-pull chromophores derived from click-type [2 + 2] cycloaddition-retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes.

Various push-pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions involving diverse electron-rich alkynes and electron-deficient alkenes. In this review, a comprehensive investigation of the recent and noteworthy advancements in the research on push-pull chromophores prepared via the [2 + 2] CA-RE reaction is conducted. In particular, an overview of the physicochemical properties of the family of these compounds that have been investigated is provided to clarify their potential for future applications.

Novel Single Emissive Component Tridurylboron-TPU Solid Polymer Ratiometric Fluorescence Thermometers.

Temperature measurements with high spatial resolution and accuracy can provide crucial data for understanding the changing process of microregion. Non-contact ratiometric fluorescence thermometers have received widespread attention for their sensitivity and interference resistibility. However, polymer and organic dye thermometers with such ratiometric fluorescence are very rare, and their applicability and processability are limited. In this study, novel tridurylboron compounds PPB1, PPB2, and PPB3 are designed and synthesized. They exhibit significant temperature responsive ratiometric fluorescence when dispersed in thermoplastic polyurethane elastomers (TPU). With a self-referencing feature and protection of TPU solid polymer, such fluorescence thermometers possess strong interference resistibility. From -10° to 60 °C, the fluorescence peak of PPB1-TPU system redshifted by 41 nm, the fluorescence color changes from blue to green. For the fluorescence ratiometric temperature measurement procedure, the absolute sensitivity is 14.5% °C-1 (40 °C) and relative sensitivity is 6.3% °C-1 (35 °C), which is much higher than reported solid polymer fluorescence thermometers. The temperature-responsive ranges can be adjusted by altering the types of polymer substrate and the number of the substituents. Such tridurylboron-TPU polymer fluorescence thermometers can be applied in aqueous environment and processed into devices of various shapes and sizes, demonstrating great potential for application.