Effect of Electron-donating Group on NO Photolysis of {RuNO}6 Ruthenium Nitrosyl Complexes with N2 O2 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) (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)→π*(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.

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. 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.

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 (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.

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. 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.

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 (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.

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. 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.

Visible-light NO photolysis of ruthenium nitrosyl complexes with N2O2 ligands bearing π-extended rings and their photorelease dynamics.

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) → 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.

Exciton Transfer at Heterointerfaces of MoS2 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 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.

Circularly Polarized Luminescence Active Supramolecular Nanotubes Based on PtII 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 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 570 nm. Meanwhile, the nanotubes, which are the thermodynamic products, show intense CPL signals (glum =±5.6×10-2 ) at 610 nm accompanied by helicity inversion. This study provides an efficient way to develop highly dissymmetric CPL nanomaterials by regulating the morphology of metallosupramolecular architectures.

Green-Light-Driven Fe(III)(btz)3 Photocatalysis in the Radical Cationic [4+2] Cycloaddition Reaction.

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.

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. 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).

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}6 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) (= 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) 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.

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. 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.

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 [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.

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. 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.

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 (gPL). In this study, we developed a molecular strategy to circumvent this trade-off. Our approach takes advantage of the strong propensity of [Pt(N^C^N)Cl], where the N^C^N ligand is 1-(2-oxazoline)-3-(2-pyridyl)phenylate, to form face-to-face stacks. We introduced chiral substituents, including (S)-methyl, (R)- and (S)-isopropyl, and (S)-indanyl groups, into the ligand framework. This asymmetric control induces torsional displacements that give homohelical stacks of the Pt(II) complexes. X-ray single-crystal structure analyses for the (S)-isopropyl Pt(II) complex reveal the formation of a homohelical dimer with a Pt···Pt distance of 3.48 Å, which is less than the sum of the van der Waals radii of Pt. This helical stack elicits the metal-metal-to-ligand charge-transfer (MMLCT) transition that exhibits strong chiroptical activity due to the electric transition moment making an acute angle to the magnetic transition moment. The PLQY and gPL values of the MMLCT phosphorescence emission of the (S)-isopropyl Pt(II) complex are 0.49 and 8.4 × 10-4, which are improved by factors of ca. 6 and 4, respectively, relative to the values of the unimolecular emission (PLQY, 0.078; gPL, 2.4 × 10-4). Our photophysical measurements for the systematically controlled Pt(II) complexes reveal that the CPL amplifications depend on the chiral substituent. Our investigations also indicate that excimers are not responsible for the enhanced chiroptical activity. To demonstrate the effectiveness of our approach, organic electroluminescence devices were fabricated. The MMLCT emission devices were found to exhibit simultaneous enhancements in the external quantum efficiency (EQE, 9.7%) and the electroluminescence dissymmetry factor (gEL, 1.2 × 10-4) over the unimolecular emission devices (EQE, 5.8%; gEL, 0.3 × 10-4). These results demonstrate the usefulness of using the chiroptically active MMLCT emission for achieving an amplified CPL.

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. The degradation model involves Langevin recombination of charge carriers on hosts, followed by the generation of a polaron pair through reductive electron transfer from a dopant to a host exciton as the initiation steps. The polarons undergo spontaneous decomposition, which competes with ultrafast recovery of the intact materials through charge recombination. Electrical and spectroscopic investigations provide information about the kinetics of each step in the operation and degradation of the devices, thereby enabling the building of mass balances for the key species in the emitting layers. Numerical solutions enable predictions of temporal decreases of the dopant concentration in various TADF emitting layers. The simulation results are in good agreement with experimental operational stabilities. This research disentangles the chemical processes in intrinsic electron-transfer degradation, and provides a useful foundation for improving the longevity of OLEDs.

Photodelivery of ß-phenylethylamines.

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

Deep-Red-Fluorescent Zinc Probe with a Membrane-Targeting Cholesterol Unit.

Organelle-targeting fluorescence probes are valuable because they can provide spatiotemporal information about the trafficking of analytes of interest. The spatiotemporal resolution can be improved by using low-energy emission signals because they are barely contaminated by autofluorescence noises. In this study, we designed and synthesized a deep-red-fluorescent zinc probe (JJ) with a membrane-targeting cholesterol unit. This zinc probe consists of a boron-azadipyrromethene (aza-BODIPY) fluorophore and a zinc receptor that is tethered to a tri(ethylene glycol)-cholesterol chain. In aqueous solutions buffered to pH 7.4, JJ exhibits weak fluorescence with a peak wavelength of 663 nm upon excitation at 622 nm. The addition of ZnCl2 elicits an approximately 5-fold enhancement of the fluorescence emission with a fluorescence dynamic range of 141000. Our electrochemical and picosecond transient photoluminescence investigations indicate that the fluorescence turn-on response is due to the zinc-induced abrogation of the formation of a nonemissive intramolecularly charge-separated species, which occurs with a driving force of 0.98 eV. The fluorescence zinc response was found to be fully reversible and to be unaffected by pH changes or the presence of biological metal ions. These properties are due to tight zinc binding with a dissociation constant of 4 pM. JJ was found to be nontoxic to HeLa cells up to submicromolar concentrations, which enables cellular imaging. Colocalization experiments were performed with organelle-specific stains and revealed that JJ is rapidly internalized into intracellular organelles, including lysosomes and endoplasmic reticula. Unexpectedly, probe internalization was found to permeabilize the cell membrane, which facilitates the influx of exogens such as zinc ions. Such permeabilization does not arise for a control probe without the tri(ethylene glycol)-cholesterol chain (JJC). Our results show that the membrane-targeting cholesterol unit can disrupt membrane integrity.