Organic Fluorescent Materials Research Articles

Pd/PTABS: Catalyst for Efficient C−H (Hetero)Arylation of 1,3,4‐Oxadiazoles Using Bromo(Hetero)Arenes

AbstractA highly efficient catalytic protocol for the C−H (hetero)arylation of 1,3,4‐oxadiazoles using low catalyst loading of Pd/PTABS system with bromo(hetero)arenes has been disclosed. The developed reaction conditions enable the synthesis of a library of differently (hetero)arylated oxadiazoles along with a commercially available fluorescent organic scintillation material, butyl‐PBD as well as anti‐tubercular agent PHOXPY. The combination of C−H arylation of oxadiazoles with Sonogashira reaction (steroidal substructures bearing alkynes), Heck alkenylation or Suzuki‐Miyaura coupling in a one‐pot tandem procedure was also made possible with an intent for new drug discovery possibilities.

Molecular and Device Design Strategies for Ideal Performance White Organic Light-Emitting Diodes.

The progress of white organic light-emitting diodes (WOLEDs) via adopting fluorescent and phosphorescent organic materials have attracted commercial interest for their broad range of visible spectrum and potential of 100 % internal quantum efficiency. In this account, smart molecular designs for developing efficient phosphorescent host and good color purity blue fluorescent emitters are prepared to be discussed, especially donor-acceptor modification to regulate their triplet states and bipolar transport properties. Rational device configuration design strategies were also introduced by cooperating with efficient conventional fluorescent and thermally activated delayed fluorescent emitting molecules to achieve full exciton utilization and simplified device structures, further suggesting perspectives of potentially low-cost, ideal performance and promoted operational lifetime in WOLED devices.

Highly fluorescent materials derived from ortho-vanillin: Structural, photophysical electrochemical and theoretical studies

Small-molecule organic fluorophores are highly in demand attributed to their extensive prospective in material and biomedical applications. Particularly, luminescent π-conjugated organic molecules that possess an efficient solid-state emission are excellent candidates for optoelectronic devices. Focusing on high demand of organic fluorophores, we herein report the synthesis of three organic fluorescent materials derived from o‑vanillin, viz. an ester (F1), an azine (F2) and an azo dye (F3). Interestingly, F2 exhibited very intense luminescence in its aggregate phase due to the restriction in intra-molecular rotation (RIR), as demonstrated by solution thickening studies. Further, its Single Crystal X-ray Crystallography (SCXRD) study suggested the existence of various intra and inter molecular interactions and gave evidences for locked intra-molecular rotations of the benzene rings in the rigid conformation of the molecule. The bathochromic shift in fluorescence from solution to solid phase was confirmed by its thin-film emission spectrum, which evidences the formation of J-aggregates. The observed RIR, development of J-aggregates and high conjugation in F2 impart an excellent fluorescence in its aggregated state. Thin films of both F2 and F3 on ITO plates exhibited a bathochromic shift with a deep orange to red photoluminescence on UV excitation. Furthermore, the morphological characterization revealed the presence of clear dense grains in case of F2 and F3, while the DSC analysis indicated phase transitions of all the derivatives. As seen from dielectric measurement studies, the azo dye F3 exhibited the highest dielectric constant among the three derivatives. The electronic and photophysical data based on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) calculations are in agreement with the experimental results. All the above data clearly advocate that, the synthesized fluorophoric o‑vanillin derivatives are excellent candidates for electro-optical devices.

Chemical transfer of dissolved organic matter from surface seawater to sea spray water-soluble organic aerosol in the marine atmosphere

It is critical to understand how variations in chemical composition in surface seawater (SSW) affect the chemistry of marine atmospheric aerosols. We investigated the sea-to-air transfer of dissolved organic carbon (DOC) via cruise measurements of both ambient aerosols and SSW in the Oyashio and its coastal regions, the western subarctic Pacific during early spring. Sea spray aerosols (SSAs) were selected based on the stable carbon isotope ratio of water-soluble organic carbon (WSOC) (δ13CWSOC) and concentrations of glucose as a molecular tracer in marine aerosols together with local surface wind speed data. For both SSA and SSW samples, excitation-emission matrices were obtained to examine the transfer of fluorescent organic material. We found that the ratios of fluorescence intensity of humic-like and protein-like substances in the submicrometer SSAs were significantly larger than those in the bulk SSW (~63%). This ratio was also larger for the supermicrometer SSAs than for the SSW. The results suggest significant decomposition of protein-like DOC on a timescale of <12–24 h and/or preferential production of humic-like substances in the atmospheric aerosols regardless of the particle size. This study provides unique insights into the complex transfer of DOC from the ocean surface to the atmosphere.

From a Molecular Toolbox to a Toolbox for Photoswitchable Fluorescent Polymeric Nanoparticles

AbstractSwitchable organic fluorescent materials are attracting much interest in many fields including flexible display, information storage, anti‐counterfeit, and bioimaging, due to their prominent properties and relatively low cost. Herein, a class of novel photoswitchable fluorescent polymeric nanoparticles (PFPNs) toolbox that shows switchable full‐colored emission including white light is described. This nanoparticles toolbox consists of a series of reversibly photoswitchable and non‐PFPNs with red, green, and blue fluorescence, and is built up from three primary fluorescent dyes and a photochromic diarylethene molecule, through a facile one‐pot miniemulsion method. The as‐prepared PFPNs display the merits of high fluorescence resonance energy transfer efficiency and fluorescence quantum yield, rapid responsiveness, prominent photoreversibility, and brilliant long‐term fluorescence stability (≈6 weeks). They enable switchable emission between white light and any visible color on‐demand in both solution and film states. Their potential in complex fluorescent encryption and photoswitchable white light‐emitting diode is described and its great potential in anti‐counterfeiting technology, data encryption, and the next generation of optoelectronic materials is foreseen.

Dynamic Visualization of Stress/Strain Distribution and Fatigue Crack Propagation by an Organic Mechanoresponsive AIE Luminogen.

Stress exists ubiquitously and is critically important for the manufacturing industry. Due to the ultrasensitive mechanoresponse of the emission of 1,1,2,2,-tetrakis(4-nitrophenyl)ethane (TPE-4N), a luminogen with aggregation-induced emission characteristics, the visualization of stress/strain distributions on metal specimens with a pure organic fluorescent material is achieved. Such a fluorescence mapping method enjoys the merits of simple setup, real-time, full-field, on-site, and direct visualization. Surface analysis shows that TPE-4N can form a nonfluorescent, crystalline uniform film on the metal surface, which cracks into fluorescent amorphous fragments upon mechanical force. Therefore, the invisible information of the stress/strain distribution of the metal specimens are transformed to visible fluorescent signals, which generally matches well but provides more details than software simulation. Remarkably, fatigue crack propagation in stainless steel and aluminum alloy can be observed and predicted clearly, further demonstrating the ultrasensitivity and practicability of TPE-4N.

Nonconjugated Fluorescent Molecular Cages of Trinuclear Fluoroborate Complexes with Salicylaldehyde-Based Schiff Base Ligands.

Fluorescent organic materials are commonly π-conjugated planar molecules. In the present work, however, we report a novel class of nonconjugated fluorescent molecular cages of trinuclear fluoroborate complexes (nine samples) with salicylaldehyde-based Schiff base ligands. Owing to the stress from lone pair electrons of N atom in the triethylamine bridge, these B(III) complexes exhibit unusual enantiomers with a tripodlike side-single-opening structure. They emit blue, green, and red emission with large Stokes shifts (up to 159 nm) and high fluorescence quantum yields in both solution (up to 0.24) and solid state (up to 0.25), which might contribute to their strong intramolecular hydrogen bonds and weak intermolecular and intramolecular π–π interactions. Combining their advantages of nonconjugation and biocompatibility, these flexible complexes have potential applications in living cell imaging and anion hosts. We have examined the inherent relationships between their chemical structures and emission properties and afforded a new stage for the design of nonconjugated fluorescent fluoroborate complexes.

Cu-Catalyzed π-Core Evolution of Benzoxadiazoles with Diaryliodonium Salts for Regioselective Synthesis of Phenazine Scaffolds.

The Cu-catalyzed regioselective synthesis of phenazine N-oxides was realized from benzoxadiazoles and diaryliodonium salts. The process was initiated by the electrophilic arylation of benzoxadiazoles with diaryliodonium salts and followed by benzocyclization reactions. The further reduction of N-oxides in situ to phenazine scaffolds and deviation to organic fluorescent materials were readily accomplished.

Unraveling the Detailed Mechanism of Excited-State Proton Transfer.

As one of the most fundamental processes, excited-state proton transfer (ESPT) plays a major role in both chemical and biological systems. In the past several decades, experimental and theoretical studies on ESPT systems have attracted considerable attention because of their tremendous potential in fluorescent probes, biological imaging, white-light-emitting materials, and organic optoelectronic materials. ESPT is related to fluorescence properties and usually occurs on an ultrafast time scale at or below 100 fs. Consequently, steady-state and femtosecond time-resolved absorption, fluorescence, and vibrational spectra have been used to explore the mechanism of ESPT. However, based on previous experimental studies, direct information, such as transition state geometries, energy barrier, and potential energy surface (PES) of the ESPT reaction, is difficult to obtain. These data are important for unravelling the detailed mechanism of ESPT reaction and can be obtained from state-of-the-art ab initio excited-state calculations. In recent years, an increasing number of experimental and theoretical studies on the detailed mechanism of ESPT systems have led to tremendous progress. This Account presents the recent advances in theoretical studies, mainly those from our group. We focus on the cases where the theoretical studies are of great importance and indispensable, such as resolving the debate on the stepwise and concerted mechanism of excited-state double proton transfer (ESDPT), revealing the sensing mechanism of ESPT chemosensors, illustrating the effect of intermolecular hydrogen bonding on the excited-state intramolecular proton transfer (ESIPT) reaction, investigating the fluorescence quenching mechanism of ESPT systems by twisting process, and determining the size of the solute·(solvent) n cluster for the solvent-assisted ESPT reaction. Through calculation of vertical excitation energies, optimization of excited-state geometries, and construction of PES of the ESPT reactions, we provide modifications to experimentally proposed mechanisms or completely new mechanism. Our proposed new and inspirational mechanisms based on theoretical studies can successfully explain the previous experimental results; some of the mechanisms have been further confirmed by experimental studies and provided guidance for researchers to design new ESPT chemosensors. Determination of the energy barrier from an accurate PES is the key to explore the ESPT mechanism with theoretical methods. This approach becomes complicated when the charge transfer state is involved for time-dependent density functional theory (TDDFT) method and optimally tuned range-separated TDDFT provides an alternative way. To unveil the driving force of ESPT reaction, the excited-state molecular dynamics combined with the intrinsic reaction coordinate calculations can be employed. These advanced approaches should be used for further studies on ESPT systems.

Acid-Induced Shift of Intramolecular Hydrogen Bonding Responsible for Excited-State Intramolecular Proton Transfer.

The significant progress recently achieved in designing smart acid-responsive materials based on intramolecular charge transfer inspired us to utilize excited-state intramolecular proton transfer (ESIPT) for developing a turn-on acid-responsive fluorescent system with an exceedingly large Stokes shift. Two ESIPT-active fluorophores, 2-(2-hydroxyphenyl)pyridine (HPP) and 2-(2-hydroxyphenyl)benzothiazole (HBT), were fused into a novel dye (HBT-HPP) fluorescent only in the protonated state. Moreover, we also synthesized three structurally relevant control compounds to compare their steady-state fluorescence spectra and optimized geometric structures in neutral and acidic media. The results suggest that the fluorescence turn-on was caused by the acid-induced shift of the ESIPT-responsible intramolecular hydrogen bond from the HPP to HBT moiety. This work presents a systematic comparison of the emission efficiencies and basicity of HBT and HPP for the first time, thereby utilizing their differences to construct an acid-responsive smart organic fluorescent material. As a practical application, red fluorescent letters can be written using the acid as an ink on polymer film.

Self-assembly, optical and electrical properties of perylene diimide dyes bearing unsymmetrical substituents at bay position

Perylene diimides (PDIs) are one class of the most explored organic fluorescent materials due to their high luminescence efficiency, optoelectronic properties, and ready to form well-tailored supramolecular structures. However, heavy aggregation caused quenching (ACQ) effect in solid state has greatly limited their potential applications. We have easily solved this problem by chemical modification of the PDI core with only phenoxy moietie at one of the bay position. In this paper, we report two perylene bisimides with small rigid substituents, 1- phenol -N, N’-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide (PDI 1) and 1- p-chlorophenol-N, N’-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide (PDI 2) possess both well defined organic nanostructures and high fluorescence quantum yield in the solid state. In contrast, 1-propanol-N, N’-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide (PDI 3) bearing a straight chain only shown weak orange fluorescence. In addition, morphological inspection demonstrated that PDI 3 molecules easily form well-organized microstructures despite the linkage of the PDI core with a straight chain. The present strategy could provide a generic route towards novel and advanced fluorescent materials and these materials may find various applications in high-tech fields.

(Invited) Alternating Current Electroluminescence for Stimuli-Interactive Sensing Display

Development of stimuli-interactive display capable of spontaneously visualizing various external human sensible inputs has been of great interest and tremendous efforts are devoted to the visualization of nonvisible human senses such as touch, smell, taste, and sound. Field induced electroluminescence of either organic or inorganic fluorescent materials under alternating current (AC) has been extensively studied and its unique device architecture in which an emitting layer is separated with an insulator from electrode offers a new platform for designing and developing emerging stimuli-interactive displays. In this presentation, high-performance field-induced AC polymer electroluminescence (AC-PEL) devices are demonstrated with high brightness, high efficiency and color and intensity-tunability. We also present a pressure interactive AC display sensor that allows for both sensing and visualisation of pressure. Light emission upon exposure to an AC field between two electrodes is controlled by the capacitance change of the insulator arising from the pressure applied on top. Besides capacitive pressure sensing, our EL sensor allows for direct visualisation of the static and dynamic information of position, shape, and size of a pressurising object on a non-pixelated single device platform. Finally, the presentation shows that simultaneous sensing and visualization of the conductive substance is achieved when the conductive object is coupled with the light emissive material layer on our novel parallel-type AC-PEL device. A variety of conductive materials can be detected regardless of their work functions, and thus information written by a conductive pen is clearly visualized, as is a human fingerprint with natural conductivity.

Precipitation of thin-film organic single crystals by a novel crystal growth method using electrospray and ionic liquid film

We report an organic single crystal growth technique, which uses a nonvolatile liquid thin film as a crystal growth field and supplies fine droplets containing solute from the surface of the liquid thin film uniformly and continuously by electrospray deposition. Here, we investigated the relationships between the solute concentration of the supplied solution and the morphology and size of precipitated crystals for four types of fluorescent organic low molecule material [tris(8-hydroxyquinoline)aluminum (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), and N,N-bis(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB)] using an ionic liquid as the nonvolatile liquid. As the concentration of the supplied solution decreased, the morphology of precipitated crystals changed from dendritic or leaf shape to platelike one. At the solution concentration of 0.1 mg/ml, relatively large platelike single crystals with a diagonal length of over 100 µm were obtained for all types of material. In the experiment using ionic liquid and dioctyl sebacate as nonvolatile liquids, it was confirmed that there is a clear positive correlation between the maximum volume of the precipitated single crystal and the solubility of solute under the same solution supply conditions.

Aggregation-induced-emission-active vinamidinium salts with tunable emissions, reversible mechanochromic response and the application in data-security protection

The development of aggregation-induced-emission (AIE)-active and reversible mechanochromic fluorescent organic materials has been of great interest in recent years because of their potential and practical application in many fields. Five vinamidinium salts that bear different aryl substitutes (Ar = phenyl (N1), p-methylphenyl (N2), p-bromophenyl (N3), p-nitrophenyl (N4) and naphthyl (N5)) were designed and synthesized. Their photophysical properties were investigated via a series of spectroscopic and theoretical methods. All compounds exhibit intense 1π-π*/intramolecular charge-transfer (1ICT) absorption bands in the region from ca. 300 nm–450 nm. All compounds except N5 display aggregation induced enhanced emission behavior in DMSO-CH2Cl2 mixtures, and relatively high quantum efficiency in solid-states (ΦF = 0.06–0.22). Compounds N1 and N3 with yellow and orange solid fluorescence, respectively, show mechanochromic and vapochromic response. Upon grinding, the emission of N1 and N3 could be transformed to green–yellow and yellow, respectively, and restored when the ground powders were fumed with MeOH vapor. Powder X-ray diffraction spectroscopy indicates that the reversible mechanochromism is ascribed to the transformation of a crystalline state into an amorphous state. Compound N1 is used in data-security protection and is of assistance in the rational design of smart luminescent materials.

Light emission from organic single crystals operated by electrolyte doping

Light-emitting devices based on electrolytes, such as light-emitting electrochemical cells (LECs) and electric double-layer transistors (EDLTs), are solution-processable devices with a very simple structure. Therefore, it is necessary to apply this device structure into highly fluorescent organic materials for future printed applications. However, owing to compatibility problems between electrolytes and organic crystals, electrolyte-based single-crystal light-emitting devices have not yet been demonstrated. Here, we report on light-emitting devices based on organic single crystals and electrolytes. As the fluorescent materials, α,ω-bis(biphenylyl)terthiophene (BP3T) and 5,6,11,12-tetraphenylnaphthacene (rubrene) single crystals were selected. Using ionic liquids as electrolytes, we observed clear light emission from BP3T LECs and rubrene EDLTs.

Tailoring the morphology of AIEgen fluorescent nanoparticles for optimal cellular uptake and imaging efficacy.

The rational design of robust fluorescent organic materials for long-term cell tracing is still challenging, and aggregation-caused quenching of emission is a big limitation of this strategy. Organic dyes with aggregation-induced emission (AIE) can effectively address this problem. Herein, AIEgen-containing nanoparticles, with different morphologies and emission, were prepared by assembling amphiphilic copolymers with an AIEgen. We compared the physical and chemical properties of rod-like and spherical nanoparticles, particularly investigating the effects of the shape on internalization and the imaging effect. The formulated nanoparticles exhibit advantageous features, such as a large Stokes shift, robust stability in physiological conditions, strong fluorescent emission, and photobleaching resistance. Interestingly, the rod-like nanoparticles were internalized more efficiently than their spherical counterparts, and their strong green fluorescence can still be clearly observed even after 15 days in vitro and in vivo. This work demonstrates the great potential of regulating the morphology of nanoparticles to obtain an ideal biological function.

Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State

Abstract4‐(Anthracen‐9‐yl)‐N,N‐diphenylaniline (TPA‐AN) is a typical molecule belonging to a donor–acceptor system. Here, the ordered crystal and the powder of TPA‐AN are used for high‐pressure Raman and fluorescence experiments, and their spectroscopic features under the shearing force of grinding and the hydrostatic pressure applied by a diamond anvil cell (DAC) are compared. The mechanochromism of TPA‐AN is discussed in detail based on the analysis of its single‐crystal structure and pressure‐driven spectral changes. During the DAC compression process, the TPA‐AN crystal shows an obvious emission band shift (from 476 to 600 nm) along with a new intramolecular charge transfer state that is separated from the hybridized local and charge transfer excited state and extremely sensitive to external force. Once the pressure is relieved, the Raman and fluorescence spectra both entirely self‐recover without a secondary force. To the authors' knowledge, TPA‐AN crystal is one of the largest emission shift organic mechanochromic fluorescent materials among reported publications. The reversible mechanochromic property of TPA‐AN for a wide‐range emission shift implies a great application potential as smart stimuli‐responsive layer in the fields of sensing, organic light‐emitting diode displays, and data storage.

Triarylborane-Based Materials for OLED Applications.

Multidisciplinary research on organic fluorescent molecules has been attracting great interest owing to their potential applications in biomedical and material sciences. In recent years, electron deficient systems have been increasingly incorporated into fluorescent materials. Triarylboranes with the empty p orbital of their boron centres are electron deficient and can be used as strong electron acceptors in conjugated organic fluorescent materials. Moreover, their applications in optoelectronic devices, energy harvesting materials and anion sensing, due to their natural Lewis acidity and remarkable solid-state fluorescence properties, have also been investigated. Furthermore, fluorescent triarylborane-based materials have been commonly utilized as emitters and electron transporters in organic light emitting diode (OLED) applications. In this review, triarylborane-based small molecules and polymers will be surveyed, covering their structure-property relationships, intramolecular charge transfer properties and solid-state fluorescence quantum yields as functional emissive materials in OLEDs. Also, the importance of the boron atom in triarylborane compounds is emphasized to address the key issues of both fluorescent emitters and their host materials for the construction of high-performance OLEDs.

A 21 000-year record of fluorescent organic matter markers in the WAIS Divide ice core

Abstract. Englacial ice contains a significant reservoir of organic material (OM), preserving a chronological record of materials from Earth's past. Here, we investigate if OM composition surveys in ice core research can provide paleoecological information on the dynamic nature of our Earth through time. Temporal trends in OM composition from the early Holocene extending back to the Last Glacial Maximum (LGM) of the West Antarctic Ice Sheet Divide (WD) ice core were measured by fluorescence spectroscopy. Multivariate parallel factor (PARAFAC) analysis is widely used to isolate the chemical components that best describe the observed variation across three-dimensional fluorescence spectroscopy (excitation–emission matrices; EEMs) assays. Fluorescent OM markers identified by PARAFAC modeling of the EEMs from the LGM (27.0–18.0 kyr BP; before present 1950) through the last deglaciation (LD; 18.0–11.5 kyr BP), to the mid-Holocene (11.5–6.0 kyr BP) provided evidence of different types of fluorescent OM composition and origin in the WD ice core over 21.0 kyr. Low excitation–emission wavelength fluorescent PARAFAC component one (C1), associated with chemical species similar to simple lignin phenols was the greatest contributor throughout the ice core, suggesting a strong signature of terrestrial OM in all climate periods. The component two (C2) OM marker, encompassed distinct variability in the ice core describing chemical species similar to tannin- and phenylalanine-like material. Component three (C3), associated with humic-like terrestrial material further resistant to biodegradation, was only characteristic of the Holocene, suggesting that more complex organic polymers such as lignins or tannins may be an ecological marker of warmer climates. We suggest that fluorescent OM markers observed during the LGM were the result of greater continental dust loading of lignin precursor (monolignol) material in a drier climate, with lower marine influences when sea ice extent was higher and continents had more expansive tundra cover. As the climate warmed, the record of OM markers in the WD ice core changed, reflecting shifts in carbon productivity as a result of global ecosystem response.

Fluorescent material concentration dependency: Förster resonance energy transfer in quasi-solid state DSSCs

Forster resonance energy transfer (FRET) is critical for wide spectral absorption, an increased dye loading, and photocurrent generation of dye-sensitized solar cells (DSSCs). This process consists of organic fluorescent materials (as an energy donor), and an organic dye (as an energy acceptor on TiO2 surfaces) with quasi-solid electrolyte. The judicious choice of the energy donor and acceptor facilitates a strong spectral overlap between the emission and absorption regions of the fluorescent materials and dye. This FRET process enhances the light-harvesting characteristics of quasi-solid state DSSCs. In this study, DSSCs containing different concentrations (0, 1, and 1.5 wt%) of a fluorescent material (FM) as the energy donor are investigated using FRET. The power conversion efficiency of DSSCs containing FMs in a quasi-solid electrolyte increased by 33% over a pristine cell. The optimized cell fabricated with the quasi-solid state DSSC containing 1.0 wt% FM shows a maximum efficiency of 3.38%, with a short-circuit current density (JSC) of 4.32 mA/cm−2, and an open-circuit voltage (VOC) of 0.68 V under illumination of simulated solar light (AM 1.5G, 100 mW/cm−2).