The degradation mechanism of multi-resonance thermally activated delayed fluorescence materials.

1,4-Azaborine-based arenes are promising electroluminescent emitters with thermally activated delayed fluorescence (TADF), offering narrow emission spectra and high quantum yields due to a multi-resonance (MR) effect. However, their practical application is constrained by their limited operational stability. This study investigates the degradation mechanism of MR-TADF molecules.

Efficient photoredox catalysis in C-C cross-coupling reactions by two-coordinated Au(I) complex.

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.

Halogen Atom Transfer-Induced Homolysis of C-F Bonds by the Excited-State Boryl Radical.

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 -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.

Charge-recombinative triplet sensitization of alkenes for DeMayo-type [2 + 2] cycloaddition.

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.

Layer-Ordered Organooxotin Clusters for Extreme-Ultraviolet Photolithography.

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.

Effect of Electron-donating Group on NO Photolysis of {RuNO} Ruthenium Nitrosyl Complexes with N O Lgands Bearing π-Extended Rings.

In this study, we introduced the electron-donating group (-OH) to the aromatic rings of Ru(salophen)(NO)Cl (0) (salophenH =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) -salophen)(NO)Cl (1), Ru((m-OH) -salophen)(NO)Cl (2), and Ru((p-OH) -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 (d , S=1/2) and released NO radicals by photons.

Achieving Long-Wavelength Electroluminescence Using Two-Coordinate Gold(I) Complexes: Overcoming the Energy Gap Law.

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.

Enhancing Circularly Polarized Phosphorescence via Integrated Top-Down and Bottom-Up Approach.

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 (g ). Square-planar Pt(II) complexes form helical assemblies, driven by torsional strain induced by bis(nonyl) chains.

Glutathione displacement assay based on a fluorescent Au(I) complex.

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.

Artificial neural network implementation for dissolved organic carbon quantification using fluorescence intensity as a predictor in wastewater treatment plants.

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 (UV), as predictors. Optimum predictors were identified based on correlation analysis to construct models using single and multiple predictors.

Phosphorescent Ir(III) Complexes for Biolabeling and Biosensing.

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.

Visible-light NO photolysis of ruthenium nitrosyl complexes with NO ligands bearing π-extended rings and their photorelease dynamics.

NO photorelease and its dynamics for two {RuNO} complexes, Ru(salophen)(NO)Cl (1) and Ru(naphophen)(NO)Cl (2), with salen-type ligands bearing π-extended systems (salophenH = ,'-(1,2-phenylene)-bis(salicylideneimine) and naphophenH = ,'-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.

Exciton Transfer at Heterointerfaces of MoS Monolayers and Fluorescent Molecular Aggregates.

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 MoS monolayers are fabricated.

Circularly Polarized Luminescence Active Supramolecular Nanotubes Based on Pt Complexes That Undergo Dynamic Morphological Transformation and Helicity Inversion.

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 Pt 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.

Green-Light-Driven Fe(III)(btz) Photocatalysis in the Radical Cationic [4+2] Cycloaddition Reaction.

Green-light-driven Fe(btz) 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.

Triplet-triplet annihilation-based photon-upconversion to broaden the wavelength spectrum for photobiocatalysis.

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.

Shifting multi-resonance to dipolar intramolecular charge-transfer fluorescence by Lewis acid-base Interactions.

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.

A new photoactivable NO-releasing {Ru-NO} ruthenium nitrosyl complex with a tetradentate ligand containing aniline and pyridine moieties.

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) (= H 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.

Boosting Photoredox Catalysis Using a Two-Dimensional Electride as a Persistent Electron Donor.

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 [GdC]·2e electride electron donor and cyclometalated Pt(II) complex photocatalysts.

Electronic structures and optical characteristics of fluorescent pyrazinoquinoxaline assemblies and Au interfaces.

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.

Chiral polymer hosts for circularly polarized electroluminescence devices.

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.

Twist to Boost: Circumventing Quantum Yield and Dissymmetry Factor Trade-Off in Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL) enables promising applications in asymmetric photonics. However, the performances of CPL molecules do not yet meet the requirements of these applications. The shortcoming originates from the trade-off in CPL between the photoluminescence quantum yield (PLQY) and the photoluminescence dissymmetry factor ().

Modeling Electron-Transfer Degradation of Organic Light-Emitting Devices.

The operational lifetime of organic light-emitting devices (OLEDs) is governed primarily by the intrinsic degradation of the materials. Therefore, a chemical model capable of predicting the operational stability is highly important. Here, a degradation model for OLEDs that exhibit thermally activated delayed fluorescence (TADF) is constructed and validated.

Photodelivery of β-phenylethylamines.

We have developed the first photodonors for the trace amino neurotransmitters, β-phenylethylamine (DPSY1) and β-methylphenylethylamine (DPSY2). Our photodonors react rapidly with photosensitized singlet dioxygen (1O2) to yield the amines. The photodelivery of β-phenylethylamine into aqueous solutions by employing liposome scaffolds is successfully demonstrated.

Benzothiazole Synthesis: Mechanistic Investigation of an In Situ-Generated Photosensitizing Disulfide.

The use of a visible light absorbing intermediate as a photosensitizer makes a chemical process simple and sustainable, obviating the need for the use of chemical additives. Herein, the formation of a photosensitizing disulfide in benzothiazole synthesis from 2-aminothiophenol and aldehydes was proposed and confirmed through in-depth mechanistic studies. A series of photophysical and electrochemical investigations revealed that an in situ-generated disulfide photosensitizes molecular oxygen to generate the key oxidants, singlet oxygen and superoxide anion, for the dehydrogenation step.