Dual and Panchromatic Emission from N-Aryl-phenanthridinones: Extension of the Seesaw Photophysical Model with a Slight Twist.

White-light emission from a single organic molecule, known as a single white-light emitter, is a rare phenomenon and desirable property for a class of materials with potential future applications in white lighting. Since N-aryl-naphthalimides (NANs) have been shown to follow excited state behavior and unique dual or panchromatic emission through a substituent pattern prescribed via a seesaw photophysical model, this study investigates the substituent effects on the fluorescence emission of structurally related N-aryl-phenanthridinones (NAPs) dyes. Following a similar placement prescription of an electron-releasing group (ERG) and electron-withdrawing group (EWG) at the phenanthridinone core and N-aryl moiety, we discovered from time-dependent density functional theory (TD-DFT) results that NAPs show a substitution pattern opposite to NANs in order to promote S2 and higher excited states. Interestingly, 2-methoxy-5-[4-nitro-3(trifluoromethyl)phenyl]phenanthridin-6(5H)-one 6e displayed a pronounced dual and panchromatic fluorescence dye depending on the solvent. For the six dyes included in the study, full spectral information in a variety of solvents, as well as fluorescence quantum yield and lifetime are reported. TD-DFT calculations support the predicted optical behavior via mixing of S2 and S6 excited states via anti-Kasha type of emission behavior.

Selective Modulation of Internal Charge Transfer and Photoinduced Electron Transfer Processes in N-Aryl-1,8-Naphthalimide Derivatives: Applications in Reaction-Based Fluorogenic Sensing of Sulfide.

Three reaction-based fluorescent probes based on two new naphthalimide platforms were developed for the detection of H2S. A new approach in detecting H2S by the reduction of an azide to a triazene intermediate in aqueous media is reported. Given their design features, these chemodosimeters provide useful insights into the relatively unexplored area of C0 spacers between receptor:reporter components. The N-aryl-1,8-naphthalimide platform features straightforward placement of the internal charge transfer and photoinduced electron transfer (PET) modulators on the same molecule. In the three examples presented, the N-aryl component proved to be an effective photophysical device as it allows the placement of a PET modulator at the strategically important and less explored imide position of 1,8-naphthalimides. These probes or dosimetric agents demonstrated good selectivity, two-signal response, and the desirable OFF-ON fluorescence response. By implementation of both the azido and nitro group as sulfide-reactive functionalities on the same chemosensory platform in probe SNAN-3, a much broader range of H2S can be detected. Remarkably, probe SNAN-3 exhibits both a dual-emission and dual-response for the detection of sulfide in aqueous solution.

Electronic Properties and Electroluminescent OLED Performance of Panchromatic Emissive N-Aryl-2,3-naphthalimides.

This report investigates the excited-state properties of a series of N-aryl-2,3-naphthalimides along with their fabrication into OLEDs and electroluminescence measurements. The N-aryl-2,3-NIs substituted specifically with chloro, fluoro, and methoxy substituents were chosen because of their unique propensity to display two emission bands or panchromatic fluorescence. Using the Lippert-Mataga analysis along with TD-DFT calculations, the excited states were determined to be n,π* and π,π*. The TD-DFT calculations on the geometries of the excited states indicate that the excited state shows a planar structure. The origin of both the short wavelength (SW) and long wavelength (LW) emission were correlated to specific geometries such that the SW emission originates from an "angled" structure in the excited state, and LW emission originates from an excited state of coplanar structure. All of the dyes investigated readily formed good films under ultrahigh vacuum deposition. The molecular energy levels of these compounds (HOMO and LUMO) were measured with cyclic voltammetry. Band gaps were also measured in both electrochemical and optical methods and indicate that the HOMOs of these fluorophores matched well with the anode (ITO work function), and their LUMOs matched well with the cathode (LiF/Al). To compare photoluminescence of the four dyes with their potential electroluminescence, three OLED devices were designed and fabricated. The electroluminescent spectra of these devices indicate that the panchromatic fluorescence, observed in solution, shifts toward the red in the solid-state. A plausible explanation appears to stem from an inability to inject electrons to the higher LUMO+1 orbitals; a process observed in the solution phase. Hence, the short wavelength fluorescence peak, a key component to panchromatic luminescence disappears in the OLED device. The observed EL spectrum from these smaller heteroatomic architectures is on par if not more broadly emissive than rubrene (5,6,11,12-tetraphenyltetracene), a red-colored C42H28 polycyclic aromatic hydrocarbon, that displays an orange-color EL.

An abiotic fluorescent probe for cardiac troponin I.

The first ratiometric fluorescent reporter was designed for the detection of cardiac troponin I (cTnI), a key protein elicited during cardiac muscle cell death. In designing this abiotic fluorescent probe, docking simulation studies were performed to predict the probe/protein interactions along the solvent exposed regions of cTnI. Simple cuvette titration experiments in aqueous buffered solution indicate remarkable selectivity for cardiac troponin in the clinically relevant nM region versus skeletal troponin.

Frontier molecular orbital analysis of dual fluorescent dyes: predicting two-color emission in N-aryl-1,8-naphthalimides.

A 3 x 3 matrix of disubstituted N-aryl-1,8-naphthalimides was synthesized for the evaluation and discovery of dual fluorescence (DF). The matrix elements included for this study were based on a predictive model that is proposed as a seesaw balanced photophysical model. This model serves as a guide to optimize the dual fluorescence emission from N-phenyl-1,8-naphthalimides by appropriate placement of substituent groups at both the 4-position of the N-arene as well as the 4'-position of the naphthalene ring. Steady-state fluorescence studies under a variety of solvents indicate that four of the nine dyes in the matrix are dual fluorescent. To provide a more quantitative description of the model, cyclic voltammetry experiments were used to calculate HOMO/LUMO energies of the aromatic components that comprise these DF dyes and give evidence in support for potential mixing of S1 and S2 excited states. Given the difficulties in predicting excited state properties such as molecular fluorescence, this ratio of four out of nine "hits" for discovering DF signifies proof of principle for this proposed model and should provide a rational basis for the synthesis of future DF 1,8-naphthalimide systems.

Photons to Formate-A Review on Photocatalytic Reduction of CO2 to Formic Acid.

Rising levels of atmospheric carbon dioxide due to the burning and depletion of fossil fuels is continuously raising environmental concerns about global warming and the future of our energy supply. Renewable energy, especially better utilization of solar energy, is a promising method for CO2 conversion and chemical storage. Research in the solar fuels area is focused on designing novel catalysts and developing new conversion pathways. In this review, we focus on the photocatalytic reduction of CO2 primarily in its neutral pH species of carbonate to formate. The first two-electron photoproduct of carbon dioxide, a case for formate (or formic acid) is made in this review based on its value as; an important chemical feedstock, a hydrogen storage material, an intermediate to methanol, a high-octane fuel and broad application in fuel cells. This review focuses specifically on the following photocatalysts: semiconductors, phthalocyanines as photosensitizers and membrane devices and metal-organic frameworks.

Highly water-soluble monoboronic acid probes that show optical sensitivity to glucose based on 4-sulfo-1,8-naphthalic anhydride.

Two highly water-soluble monoboronic acid probes that display the more desirable off-on fluorescence response were synthesized based on 4-sulfo-1,8-naphthalic anhydride and a remarkable sensitivity for glucose rather than fructose and galactose was also observed.

A comparative study into two dual fluorescent mechanisms via positional isomers of N-hydroxyarene-1,8-naphthalimides.

Three isomers of hydroxy substituted N-aryl-1, 8-naphthalimides based on N-aryl naphthalic anhydride fluorophore have been synthesized. The decrease in fluorescence intensity from ortho to para substitution of hydroxy group on N-aryl reveals that para substituted isomer undergoes ESEC (Excited State with Extended Conjugation) mechanism which is proved by low quantum yield and appearance of dual emission. The ortho isomer, however, has high quantum yield and no tautomer emission, indicating ESIPT (Excited State Intramolecular Proton Transfer) mechanism is not operating. Similarly, all these isomers show strong fluorescence quenching in presence of strong H-bonding solvents like DMSO and pyridine, but there was neither the shift of emission bands nor the appearance of new bands for proton transfer to these solvents. Thus, it also indicates the absence of excited state proton transfer mechanism. Both the ortho isomer, and to a greater degree the meta isomer, showed larger quenching constants (Kapp) with pyridine than DMSO. This trend opposes the hydrogen-bond affinity for these solvents with phenol and points to a 2-point recognition interaction. In addition, a naphthalimide derivative using 2-aminoimidazole was prepared and examined for optimal positioning of a six-membered ring hydrogen bond pattern. No dual fluorescence was observed for this compound either.

Photocatalyzed Reduction of Bicarbonate to Formate: Effect of ZnS Crystal Structure and Positive Hole Scavenger.

Zinc sulfide is a promising catalyst due to its abundance, low cost, low toxicity and conduction band position that enables the photoreduction of CO2 to formic acid. This study is the first to examine experimentally the photocatalytic differences between wurtzite and sphalerite under the parameters of size (micrometer and nanoscale), crystal lattice, surface area, and band gap on productivity in the photoreduction of HCO3(-). These photochemical experiments were conducted under air mass coefficient zero (AM 0) and AM 1.5 solar simulation conditions. We observed little to no formate production under AM 1.5, but found linear formate production as a function of time using AM 0 conditions. Compared to earlier reports involving bubbled CO2 in the presence of bicarbonate, our results point to bicarbonate as the species undergoing reduction. Also investigated are the effects of three hydroxylic positive hole scavengers, ethylene glycol, propan-2-ol (isopropyl alcohol, IPA) and glycerol on the reduction of HCO3(-). Glycerol, a green solvent derived from vegetable oil, greatly improved the apparent quantum efficiency of the photocatalytic reduction.

Monoboronic acid sensor that displays anomalous fluorescence sensitivity to glucose.

[reaction: see text]. A monoboronic acid fluorescent sensor was conveniently synthesized from 3-nitronaphthalic anhydride and 3-aminophenylboronic acid. This novel saccharide probe exhibits dual emission suitable for ratiometric sensing and displays a remarkable sensitivity for glucose relative to fructose and galactose.

Spectroscopic and Photophysical Characterization of Fluorescent Chemosensors for Monosaccharides Based on N-Phenylboronic Acid Derivatives of 1,8-Naphthalimide.

Spectroscopic and photophysical properties of two fluorescent probes for monosaccharides are presented. Probes are based on the N-phenyl-1,8-naphthalimide structure having the boronic acid group [R-B(OH)2] in ortho in one case, and meta in the other case, positions of the N-phenyl group. Formation of the anionic form of the boronic acid group [ R-B ( OH ) 3 - ] induced a substantial decrease of the steady-state fluorescence of both compounds. Because no change in the fluorescence lifetime from the neutral to the anionic forms is observed, static quenching resulting from photoinduced electron transfer from the anionic form of the boronic acid is used to explain the decrease of the emission intensity. Both compounds show substantial decreases of their fluorescence intensity in the presence of sugars. In addition, this decrease of the fluorescence intensity is associated with an increase of the fluorescence lifetime for the ortho derivative while no effect on the lifetime is observed for the meta derivative. Both photoinduced electron transfer and steric hindrance are discussed to correlate the observed results.

An organic white light-emitting dye: very small molecular architecture displays panchromatic emission.

The synthesis and photophysical characterization of a new white-light fluorophore is described. The optimization of excitation wavelengths allows the naphthalimide (NI) dyes to display blue, green or white light emission depending on the excitation wavelength.

Dual fluorescent N-aryl-2,3- naphthalimides: applications in ratiometric DNA detection and white organic light-emitting devices.

A ten element matrix of 5- and 6-substituted-(2,3)-naphthalimides was prepared for the appropriate placement of substituents necessary to promote dual fluorescence (DF). As prescribed by our balanced seesaw photophysical model this matrix yielded nine new DF dyes out of a possible ten compounds. From this set of nine DF dyes, 4-fluoronaphthalic amide (37) was selected as a probe for ratiometric detection of DNA and demonstration of panchromatic emission.

Discovery of dual fluorescent 1,8-naphthalimide dyes based on balanced seesaw photophysical model.

The 3 x 3 matrix elements included for the evaluation of dual fluorescence are based on a predictive model described as a 'seesaw balanced' photophysical model.

Toward intrinsically fluorescent proteomimetics: fluorescent probe response to alpha helix structure of poly-gamma-benzyl-L-glutamate.

A fluorescent probe (1), developed for recognition of alpha helical secondary structure, shows a large fluorescence change upon titration with the synthetic protein PBLG. Compared to fluorophores of similar size and shape, 1 displayed the smallest dissociation constant (K(D)=80microM) when titrated with PBLG. These preliminary studies are directed toward developing small molecule proteomimetics that have intrinsic fluorescence and are specific for helical-protein binding-sites.

Matrix screening of substituted N-aryl-1,8-naphthalimides reveals new dual fluorescent dyes and unusually bright pyridine derivatives.

A 3 x 14 matrix of substituted N-aryl-1,8-naphthalimides was synthesized for the evaluation and discovery of dual fluorescence. Because of their unique photophysical properties, these dual fluorescent systems represent an exception to the widely studied TICT (Twisted Internal Charge Transfer) fluorescent dyes or tautomeric benzofluorescein class of two-color dyes. The matrix library was designed to investigate the effects of heterocycles, particularly pi-excessive and pi-deficient systems. Of the 42 compounds surveyed, five displayed well-resolved two-color emission in solvents as nonpolar as hexane. Based on the observed trends in fluorescence lambda(max) and quantum yield, a new model is proposed that predicts LW and SW emission for these systems. In addition, this model provides potential design features for the synthesis of new dual fluorescent species.

Fluorescent chemosensors for carbohydrates: a decade's worth of bright spies for saccharides in review.

This review provides a chronological survey of over fifty fluorescent chemosensors for carbohydrates from the period between 1992 to the present. The survey contains only those sensors that are synthetic or chemosensory, utilize boronic acids and display a fluorescence response in the form of intensity changes or shifts in wavelength. With each compound listed, a description of the saccharide probe is given with regard to concentration, excitation and emission wavelengths, pH and solvent mixture proportions. In addition, the selectivity of each chemosensor is provided as well as the trends in binding constants. Where possible, a description of the fluorescence signaling mechanism is given as well as commentary on the probe's unique features within this class of sensors.

Substituent effects on monoboronic acid sensors for saccharides based on N-phenyl-1,8-naphthalenedicarboximides.

In the course of our investigations on new monoboronic acid saccharide sensors with C(0) spacers, a series of probes 1-6 based on 1,8-naphthalenedicarboximide were synthesized. Sensor 1 displays features typical of PET monoboronic acid sensors and shows high selectivity to fructose. Sensor 2 exhibits a novel dual emission and remarkable sensitivity for glucose relative to fructose and galactose through subtle changes in pH. Sensor 3 displays significantly enhanced fluorescence in the presence of galactose at low pH. Although probes 4-6 exhibit unique properties such as high quantum yield (Phi(F) = 0.407) and excellent solubility in water, they did not show significant change in fluorescence intensity in the presence of monosaccharides. The effects of substituent on all six probes lend support to the proposed photoelectrochemical model.