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Photocatalysis provides a versatile approach to redox activation of various organic substrates for synthetic applications. To broaden the scope of photoredox catalysis, developing catalysts with strong oxidizing or reducing power in the excited state is imperative. Catalysts that feature highly cathodic oxidation potentials and long lifetimes in their excited states are particularly in demand. In this research, we demonstrate the catalytic utility of two-coordinate Au(I) complex photocatalysts that exhibit an exclusive ligand-to-ligand charge-transfer (LLCT) transition in C-C cross-coupling reactions between N-heterocycles and (hetero)aryl halides, including redox-resistant (hetero)aryl chlorides. Our photocatalysis system can steer reactions under visible-light irradiation at a catalyst loading as low as 0.1 mol% and exhibits a broad substrate scope with high chemo- and regioselectivity. Our mechanistic investigations provide direct spectroscopic evidence for each step in the catalysis cycle and demonstrate that the LLCT-active Au(I) complex catalysts offer several benefits, including strong visible-light absorption, a 210 ns-long excited-state lifetime without short-lived components, and a 91% yield in the production of free-radical intermediates. Given the wide structural versatility of the proposed catalysts, we envision that our research will provide useful insights into the future utilization of the LLCT-active Au(I) complex for organic transformations.
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Synthetic photochemistry has undergone significant development, largely owing to the development of visible-light-absorbing photocatalysts (PCs). PCs have significantly improved the efficiency and precision of cycloaddition reactions, primarily through energy or electron transfer pathways. Recent research has identified photocatalysis that does not follow energy- or electron-transfer formalisms, indicating the existence of other, undiscovered photoactivation pathways. This study unveils an alternative route: a charge-neutral photocatalytic process called charge-recombinative triplet sensitization (CRTS), a mechanism with limited precedents in synthetic chemistry. Our investigations revealed CRTS occurrence in DeMayo-type [2 + 2] cycloaddition reactions catalyzed by indole-fused organoPCs. Our mechanistic investigations, including steady-state and transient spectroscopic analyses, electrochemical investigations, and quantum chemical calculations, suggest a mechanism involving substrate activation through photoinduced electron transfer, followed by charge recombination, leading to substrate triplet state formation. Our findings provide valuable insights into the underlying photocatalytic reaction mechanisms and pave the way for the systematic design and realization of innovative photochemical processes.
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A novel reactivity toward C-F bond functionalization has been developed, which could be designated as fluorine atom transfer (FAT). A photoexcited state of an N-heterocyclic carbene-ligated boryl radical exhibits a transcendent reactivity, capable of activating chemically inert carbon-fluorine bonds through homolysis. Combined experimental and computational studies suggest that the ligated boryl radical species directly abstracts a fluorine atom from the organofluoride substrates to provide valuable carbon-centered radicals.
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Extreme-ultraviolet (EUV) photolithography, which enables the high-throughput production of well-defined patterns with critical dimensions on the scale of several nanometers, is essential for the fabrication of a highly integrated semiconductor. The full exploitation of EUV lithographic techniques necessitates the development of photoresist (PR) materials with both high EUV sensitivity and a long shelf-life. However, despite notable advances, the available library of EUV PR materials remains limited. Here we report EUV PRs capable of forming preorganized layers consisting of ladder-structured tetranuclear stannoxanes. Single-crystal X-ray structure analyses reveal a close interlayer distance of 8.5 Å through interdigitation of the pseudoaxial butyl chains. The developed EUV PR materials exhibit high solubility in organic solvents commonly used in semiconductor processing, enabling the preparation of PR solutions with superior wettability and uniform film-forming ability on Si wafer substrates. These PR solutions also demonstrate notable resistance to hydrolytic decomposition for as long as 1 month, indicating a long shelf-life. Our PR materials enabled negative-tone patterning processes that involved a solubility decrease upon irradiation. The presence of chromophoric ligands makes our PR materials compatible with conventional UV photolithography, through photochemical reactions involving carbonyl units. In addition, e-beam and EUV lithography could produce fine line patterns of our PRs, with critical dimensions of 20 and 15 nm, respectively. Our research showcases the potential of layer-ordered organooxotin clusters for EUV PR applications.
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Two-coordinate coinage metal complexes have emerged as promising emitters for highly efficient organic light-emitting devices (OLEDs). However, achieving efficient long-wavelength electroluminescence emission from these complexes remains as a daunting challenge. To address this challenge, molecular design strategies aimed at bolstering the photoluminescence quantum yield (Φ) of Au(I) complex emitters in low-energy emission regions are investigated. By varying amido ligands, a series of two-coordinate Au(I) complexes is developed that exhibit photoluminescence peak wavelengths over a broad range of 533-750 nm. These complexes, in particular, maintain Φ values up to 10% even in the near-infrared emission region, overcoming the constraints imposed by an energy gap. Quantum chemical calculations and photophysical analyses reveal the action of radiative control, which serves to overcome the energy gap law, becomes more pronounced as the overlap between hole and electron distributions (Sr (r)) in the excited state increases. It is further elucidated that Sr (r) increases with the distance between the hole-distribution centroid and the nitrogen atom in an amido ligand. Finally, multilayer OLEDs involving the Au(I) complex emitters exhibit performances beyond the borderline of the electroluminescence wavelength-external quantum efficiency space set by previous devices of coinage metal complexes.
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In this study, we introduced the electron-donating group (-OH) to the aromatic rings of Ru(salophen)(NO)Cl (0) (salophenH2 =N,N'-(1,2-phenylene)bis(salicylideneimine)) to investigate the influence of the substitution on NO photolysis and NO-releasing dynamics. Three derivative complexes, Ru((o-OH)2 -salophen)(NO)Cl (1), Ru((m-OH)2 -salophen)(NO)Cl (2), and Ru((p-OH)2 -salophen)(NO)Cl (3) were developed and their NO photolysis was monitored by using UV/Vis, EPR, NMR, and IR spectroscopies under white room light. Spectroscopic results indicated that the complexes were diamagnetic Ru(II)-NO+ species which were converted to low-spin Ru(III) species (d5 , S=1/2) and released NO radicals by photons. The conversion was also confirmed by determining the single-crystal structure of the photoproduct of 1. The photochemical quantum yields (ΦNO s) of the photolysis were determined to be 0>1, 2, 3 at both the visible and UV excitations. Femtosecond (fs) time-resolved mid-IR spectroscopy was employed for studying NO-releasing dynamics. The geminate rebinding (GR) rates of the photoreleased NO to the photolyzed complexes were estimated to be 0≃1, 2, 3. DFT and TDDFT computations found that the introduction of the hydroxyl groups elevated the ligand π-bonding orbitals (π (salophen)), resulting in decrease of the HOMO-LUMO gaps in 1-3. The theoretical calculations suggested that the Ru-NNO bond dissociations of the complexes were mostly initiated by the ligand-to-ligand charge transfer (LLCT) of π(salophen)âπ*(Ru-NO) with both the visible and UV excitations and the decreasing ΦNO s could be explained by the changes of the electronic structures in which the photoactivable bands of 1-3 have relatively less contribution of transitions related with Ru-NO bond than those of 0.
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In the dynamic domain of chiroptical technologies, it is imperative to engineer emitters endowed with circularly polarized luminescence (CPL) properties. This research demonstrates an advancement by employing a combined top-down and bottom-up strategy for the simultaneous amplification of photoluminescence quantum yield (Φ) and the luminescence dissymmetry factor (glum ). Square-planar Pt(II) complexes form helical assemblies, driven by torsional strain induced by bis(nonyl) chains. Integration of chiral anions leads these assemblies to prefer distinct helical sense. This arrangement activates the metal-metal-to-ligand charge transfer (MMLCT) transition that is CPL-active, with Φ and |glum | observing an upswing contingent on the charge number and aryl substituents in chiral anions. Utilizing the soft-lithographic micromolding in capillaries technique, we could fabricate exquisitely-ordered, one-dimensional co-assemblies to achieve the metrics to Φ of 0.32 and |glum | of 0.13. Finally, our spectroscopic research elucidates the underlying mechanism for the dual amplification, making a significant stride in the advancement of CPL-active emitters.
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Glutathione (GSH) is an essential molecule that plays a pivotal role in maintaining intracellular redox homeostasis, as well as other physiological processes. However, the chemical mechanisms underlying the GSH-induced processes remain insufficiently understood due to the lack of appropriate detection tools. Fluorescence GSH imaging can serve as a useful principle for the rapid, convenient, and non-destructive detection of GSH in living organisms. In this study, we developed a fluorescent GSH probe based on a linear, homoleptic Au(I) complex with two 1,3-diphenylbenzimidazolium carbene ligands. The Au(I) complex produced a fluorescence turn-on response to GSH. Fluorescence GSH signaling was characterized with a short response time of a few seconds. The rapid response was attributed to the displacement of the carbene ligand with GSH, which involved a labile inner-sphere coordination interaction. Finally, we demonstrated the biological utility of our GSH probe by unambiguously discriminating between different GSH levels in normal and senescent preadipocytes.
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Glutationa , Glutationa/química , Ouro/química , Corantes Fluorescentes/química , Concentração de Íons de Hidrogênio , Sobrevivência CelularRESUMO
Although spectroscopic methods provide a fast and cost-effective means of monitoring dissolved organic carbon (DOC) in natural and engineered water systems, the prediction accuracy of these methods is limited by the complex relationship between optical properties and DOC concentration. In this study, we developed DOC prediction models using multiple linear/log-linear regression and feedforward artificial neural network (ANN) and investigated the effectiveness of spectroscopic properties, such as fluorescence intensity and UV absorption at 254 nm (UV254), as predictors. Optimum predictors were identified based on correlation analysis to construct models using single and multiple predictors. We compared the peak-picking and parallel factor analysis (PARAFAC) methods for selecting appropriate fluorescence wavelengths. Both methods had similar prediction capability (p-values >0.05), suggesting PARAFAC was not necessary for choosing fluorescence predictors. Fluorescence peak T was identified as a more accurate predictor than UV254. Combining UV254 and multiple fluorescence peak intensities as predictors further improved the prediction capability of the models. The ANN models outperformed the linear/log-linear regression models with multiple predictors, achieving higher prediction accuracy (peak-picking: R2 = 0.8978, RMSE = 0.3105 mg/L; PARAFAC: R2 = 0.9079, RMSE = 0.2989 mg/L). These findings suggest the potential to develop a real-time DOC concentration sensor based on optical properties using an ANN for signal processing.
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Poluentes Químicos da Água , Purificação da Água , Matéria Orgânica Dissolvida , Espectrometria de Fluorescência/métodos , Poluentes Químicos da Água/análise , Purificação da Água/métodos , ÁguaRESUMO
Cyclometalated Ir(III) complexes exhibit strong phosphorescence emission with lifetime of submicroseconds to several microseconds at room temperature. Their synthetic versatility enables broad control of physical properties, such as charge and lipophilicity, as well as emission colors. These favorable properties have motivated the use of Ir(III) complexes in luminescent bioimaging applications. This review examines the recent progress in the development of phosphorescent biolabels and sensors based on Ir(III) complexes. It begins with a brief introduction about the basic principles of the syntheses and photophysical processes of cyclometalated Ir(III) complexes. Focus is placed on illustrating the broad imaging utility of Ir(III) complexes. Phosphorescent labels illuminating intracellular organelles, including mitochondria, lysosomes, and cell membranes, are summarized. Ir(III) complexes capable of visualization of tumor spheroids and parasites are also introduced. Facile chemical modification of the cyclometalating ligands endows the Ir(III) complexes with strong sensing ability. Sensors of temperature, pH, CO2, metal ions, anions, biosulfur species, reactive oxygen species, peptides, and viscosity have recently been added to the molecular imaging tools. This diverse utility demonstrates the potential of phosphorescent Ir(III) complexes toward bioimaging applications.
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Irídio , Luminescência , Íons , Irídio/química , Ligantes , Imagem MolecularRESUMO
NO photorelease and its dynamics for two {RuNO}6 complexes, Ru(salophen)(NO)Cl (1) and Ru(naphophen)(NO)Cl (2), with salen-type ligands bearing π-extended systems (salophenH2 = N,N'-(1,2-phenylene)-bis(salicylideneimine) and naphophenH2 = N,N'-1,2-phenylene-bis(2-hydroxy-1-naphthylmethyleneimine)) were investigated. NO photolysis was performed under white room light and monitored by UV/Vis, EPR, and NMR spectroscopies. NO photolysis was also performed under 459 and 489 nm irradiation for 1 and 2, respectively. The photochemical quantum yields of the NO photolysis (ΦNO) of both 1 and 2 were determined to be 9% at the irradiation wavelengths. The structural and spectroscopic characteristics of the complexes before and after the photolysis confirmed the conversion of diamagnetic Ru(II)(L)(Cl)-NO+ to paramagnetic S = ½ Ru(III)(L)(Cl)-solvent by photons (L = salophen2- and naphophen2-). The photoreleased NO radicals were detected by spin-trapping EPR. DFT and TDDFT calculations found that the photoactive bands are configured as mostly the ligand-to-ligand charge transfer (LLCT) of π(L) â π*(Ru-NO), suggesting that the NO photorelease was initiated by the LLCT. Dynamics of NO photorelease from the complexes in DMSO under 320 nm excitation were investigated by femtosecond (fs) time-resolved mid-IR spectroscopy. The primary photorelease of NO occurred for less than 0.32 ps after the excitation. The rate constants (k-1) of the geminate rebinding of NO to the photolyzed 1 and 2 were determined to be (15 ps)-1 and (13 ps)-1, respectively. The photochemical quantum yields of NO photolysis (ΦNO, λ = 320 nm) were estimated to be no higher than 14% for 1 and 11% for 2, based on the analysis of the fs time-resolved IR data. The results of fs time-resolved IR spectroscopy and theoretical calculations provided some insight into the overall kinetic reaction pathway, localized electron pathway or resonance pathway, of the NO photolysis of 1 and 2. Overall, our study found that the investigated {RuNO}6 complexes, 1 and 2, with planar N2O2 ligands bearing π-extended rings effectively released NO under visible light.
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Circularly polarized luminescence (CPL) with tunable chirality is currently a challenging issue in the development of supramolecular nanomaterials. We herein report the formation of helical nanoribbons which grow into helical tubes through dynamic helicity inversion. For this, chiral PtII complexes of terpyridine derivatives, namely S-trans-1 and R-trans-1, with respective S- and R-alanine subunits and incorporating trans-double bonds in the alkyl chain were prepared. In DMSO/H2 O (5 : 1 v/v), S-trans-1 initially forms a fibrous self-assembled product, which then undergoes dynamic transformation into helical tubes (left-handed or M-type) through helical ribbons (right-handed or P-type). Interestingly, both helical supramolecular architectures are capable of emitting CPL signals. The metastable helical ribbons show CPL signals (glum =±4.7×10-2 ) at 570â nm. Meanwhile, the nanotubes, which are the thermodynamic products, show intense CPL signals (glum =±5.6×10-2 ) at 610â nm accompanied by helicity inversion. This study provides an efficient way to develop highly dissymmetric CPL nanomaterials by regulating the morphology of metallosupramolecular architectures.
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Photobiocatalysis is a growing field of biocatalysis. Especially light-driven enzyme catalysis has contributed significantly to expanding the scope of synthetic organic chemistry. However, photoenzymes usually utilise a rather narrow wavelength range of visible (sun)light. Triplet-triplet annihilation-based upconversion (TTA-UC) of long wavelength light to shorter wavelength light may broaden the wavelength range. To demonstrate the feasibility of light upconversion we prepared TTA-UC poly(styrene) (PS) nanoparticles doped with platinum(II) octaethylporphyrin (PtOEP) photosensitizer and 9,10-diphenylanthracene (DPA) annihilator (PtOEP:DPA@PS) for application in aqueous solutions. Photoexcitation of PtOEP:DPA@PS nanoparticles with 550 nm light led to upconverted emission of DPA 418 nm. The TTA-UC emission could photoactivate flavin-dependent photodecarboxylases with a high energy transfer efficiency. This allowed the photodecarboxylase from Chlorella variabilis NC64A to catalyse the decarboxylation of fatty acids into long chain secondary alcohols under green light (λ = 550 nm).
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Chlorella , Nanopartículas , Transferência de Energia , Fótons , Fármacos FotossensibilizantesRESUMO
Integration of distinct materials to form heterostructures enables the proposal of new functional devices based on emergent physical phenomena beyond the properties of the constituent materials. The optical responses and electrical transport characteristics of heterostructures depend on the charge and exciton transfer (CT and ET) at the interfaces, determined by the interfacial energy level alignment. In this work, heterostructures consisting of aggregates of fluorescent molecules (DY1) and 2D semiconductor MoS2 monolayers are fabricated. Photoluminescence spectra of DY1/MoS2 show quenching of the DY1 emission and enhancement of the MoS2 emission, indicating a strong electronic interaction between these two materials. Nanoscopic mappings of the light-induced contact potential difference changes rule out the CT process at the interface. Using femtosecond transient absorption spectroscopy, the rapid interfacial ET process from DY1 aggregates to MoS2 and a fourfold extension of the exciton lifetime in MoS2 are elucidated. These results suggest that the integration of 2D inorganic semiconductors with fluorescent molecules can provide versatile approaches to engineer the physical characteristics of materials for both fundamental studies and novel optoelectronic device applications.
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Green-light-driven FeIII(btz)3 photocatalysis for the radical cationic [4+2] cycloaddition of terminal styrenes and nucleophilic dienes has been investigated. The Fe-MIC (mesoionic carbene) complex forms a ligand-to-metal charge-transfer transition state with relatively high excited-state reduction potentials that can selectively oxidize terminal styrene derivatives. Unique multisubstituted cyclohexenes and structurally complex biorelevant cyclohexenes were constructed, highlighting the usefulness of this mild and practical first-row transition metal complex system.
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Compostos Férricos , Elementos de Transição , Cátions , Reação de Cicloadição , Cicloexenos , LuzRESUMO
Lewis acid-base interactions of 1-hydroxy-10-phenylacridone produce large chromic shifts in fluorescence, due to a change in a multi-resonance intramolecular charge-transfer (ICT) character to a dipolar ICT character.
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Ácidos de Lewis , Bases de Lewis , Espectrometria de Fluorescência , VibraçãoRESUMO
A new type of photoactivable NO-releasing ruthenium nitrosyl complex, [Ru(EPBP)Cl(NO)], with a tetradentate ligand, N,N'-(ethane-1,2-diyldi-o-phenylene)-bis(pyridine-2-carboxamide) (= H2 EPBP) was synthesized. Single crystal X-ray crystallography revealed that the complex has a distorted octahedral coordination geometry and NO is positioned at cis to Cl- ion. NO-photolysis was observed under a white room light. The photodissociation of Ru-NO bond was identified by various techniques including X-ray crystallography, IR, UV/Vis absorption, electron paramagnetic resonance (EPR), and NMR spectroscopies. Quantum yields for the NO-photolysis of the complex in CH3 OH, CHCl3 , DMSO, CH3 CN, and CH3 NO2 were measured to be 0.19-0.36 with 400 (±5)â nm excitation. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations were performed to understand the details of the photodissociation of the complex. The calculations suggest that the NO photolysis is most likely initiated by the electronic transition from the aniline moiety π MOs (π (aniline)) of the EPBP2- chelating ligand to the π-antibonding MO of Ru-NO (π*(Ru-NO)). Experimental and theoretical investigations indicate that the EPBP2- ligand provides an effective platform forming ruthenium nitrosyl complexes useful for NO-photoreleasing.
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Rutênio , Compostos de Anilina , Cristalografia por Raios X , Ligantes , PiridinasRESUMO
Understanding the excitonic processes at the interfaces of fluorescent π-conjugated molecules and metal electrodes is important for both fundamental studies and emerging applications. Adsorption configurations of molecules on metal surfaces significantly affect the physical characteristics of junctions as well as molecules. Here, the electronic structures and optical properties of molecular assemblies/Au interfaces were investigated using scanning probe and photoluminescence microscopy techniques. Scanning tunneling microscopy images and tunneling conductance spectra suggested that the self-assembled molecules were physisorbed on the Au surface. Visible-range photoluminescence studies showed that Au thin films modified the emission spectra and reduced the lifetime of excitons. Surface potential maps, obtained by Kelvin probe force microscopy, could visualize electron transfer from the molecules to Au under illumination, which could explain the decreased lifetime of excitons at the molecule/Au interface.
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Electrides, which have excess anionic electrons, are solid-state sources of solvated electrons that can be used as powerful reducing agents for organic syntheses. However, the abrupt decomposition of electrides in organic solvents makes controlling the transfer inefficient, thereby limiting the utilization of their superior electron-donating ability. Here, we demonstrate the efficient reductive transformation strategy which combines the stable two-dimensional [Gd2C]2+·2e- electride electron donor and cyclometalated Pt(II) complex photocatalysts. Strongly localized anionic electrons at the interlayer space in the [Gd2C]2+·2e- electride are released via moderate alcoholysis in 2,2,2-trifluoroethanol, enabling persistent electron donation. The Pt(II) complexes are adsorbed onto the surface of the [Gd2C]2+·2e- electride and rapidly capture the released electrons at a rate of 107 s-1 upon photoexcitation. The one-electron-reduced Pt complex is electrochemically stable enough to deliver the electron to substrates in the bulk, which completes the photoredox cycle. The key benefit of this system is the suppression of undesirable charge recombination because back electron transfer is prohibited due to the irreversible disruption of the electride after the electron transfer. These desirable properties collectively serve as the photoredox catalysis principle for the reductive generation of the benzyl radical from benzyl halide, which is the key intermediate for dehalogenated or homocoupled products.
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Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (g abs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (g PL) of the order of 10-3 were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of g abs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (g EL) of 1.09 × 10-4 and -1.02 × 10-4 at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.