Light-emitting Molecules Research Articles

Metal-organic-frameworks (MOFs) advanced synthetic strategies and applications, including light emitting diodes, solar cells and photodetectors

Abstract Several synthetic approaches, such as solvothermal, microwave-assisted, electrochemical, and mechanochemical techniques, are used in the creation of metal-organic frameworks (MOFs). The resulting MOFs can be tailored for particular purposes by utilizing the distinct benefits that each of these approaches offers in terms of managing their size, shape, and functional qualities. The most recent developments in MOF synthesis are examined in this study along with how they are being used in optoelectronic devices such as photodiodes, solar cells, and light-emitting diodes (LEDs). MOFs are potential candidates for these applications because of their special qualities, which include their capacity to host light-emitting guest molecules, promote charge transport, and improve light absorption. MOFs effectively house luminescent centers in LEDs, improving brightness and color purity. MOFs improve charge separation and light collecting efficiency in solar cells. The customizable band gaps of MOFs, which may be designed to maximize their performance in photodetection, are advantageous to photodiodes. Advances in MOFs could revolutionize future optoelectronics. Finally, MOFs are based on the ongoing development of advanced synthetic methods that allow for the fabrication of LEDs, solar cells and photodetectors at higher levels of technological innovation and application. Additionally, MOFs in photodetectors, are thought to be active material and their special capacity to interact at various wavelengths may pave the way for more sensitive and adaptable application-specific sensors in a range of areas, including high-speed communication technologies and environmental monitoring.

Modeling the electroluminescence of atomic wires from quantum dynamics simulations.

Static and time-dependent quantum-mechanical approaches have been employed in the literature to characterize the physics of light-emitting molecules and nanostructures. However, the electromagnetic emission induced by an input current has remained beyond the realm of molecular simulations. This is the challenge addressed here with the help of an equation of motion for the density matrix coupled to a photon bath based on a Redfield formulation. This equation is evolved within the framework of the driven-Liouville von Neumann approach, which incorporates open boundaries by introducing an applied bias and a circulating current. The dissipated electromagnetic power can be computed in this context from the time derivative of the energy. This scheme is applied in combination with a self-consistent tight-binding Hamiltonian to investigate the effects of bias and molecular size on the electroluminescence of metallic and semiconducting chains. For the latter, a complex interplay between bias and molecular length is observed: there is an optimal number of atoms that maximizes the emitted power at high voltages but not at low ones. This unanticipated behavior can be understood in terms of the band bending produced along the semiconducting chain, a phenomenon that is captured by the self-consistency of the method. A simple analytical model is proposed that explains the main features revealed by the simulations. The methodology, applied here at a self-consistent tight-binding level but extendable to more sophisticated Hamiltonians such as density functional tight binding and time dependent density functional theory, promises to be helpful for quantifying the power and quantum efficiency of nanoscale electroluminescent devices.

Molecular Engineering to Achieve AIE-active Fluorophore with Near-infrared (NIR) Emission and Temperature-sensitive Property.

Near-infrared organic small molecule luminescent materials have the advantages of easy modification, high quantum efficiency, good biological affinity, and color adjustability; thus, have promising application prospects in the fields of photoelectric devices, sensitive detection, photodynamic therapy, and biomedical imaging. However, traditional organic luminescent molecules have the problems of short emission wavelength, aggregation-causing emission quenching, and low quantum yield. Herein, we successfully synthesized four D-π-A-D light-emitting molecules based on electron-withdrawing malonitrile group and different electron-donating arylamine groups. These compounds showed satisfactory solvatochromism, aggregation-induced emission, red and near-infrared fluorescence, high photoluminescence quantum efficiency and temperature response properties. This successful example of molecular engineering provides a valuable reference for the development of advanced NIR materials with AIE and temperature-sensitive properties.

Donor-donor-acceptor (D-D-A) luminogens containing a central carbazole core: Aggregation-induced emission (AIE), full-color solid-state emission and diverse mechanofluorochromic characteristics

The construction of multi-functionalized luminophores with full-color emission based on the same core skeleton is an appealing yet significantly challenging task. In this work, we rationally designed and facilely constructed a series of donor-donor-acceptor (D-D-A) based luminogens by representative Suzuki-Miyaura cross-coupling reaction. Using electron-donating carbazole with hexyl chain as basic core structure, a series of donor-donor-acceptor (D-D-A) typed luminogens with different donor and acceptor units were designed and synthesized. Some compounds showed AIEE or aggregate fluorescence change behaviors due to TICT and RIM. Among them, these compounds displayed diverse mechanofluorochromic characteristics, including reversible or irreversible, red-shifted or blue-shifted mechanofluorochromisms. This provided new ideas for the development of multifunctional organic light-emitting molecules.

Understanding Organic Photovoltaic Materials Using Simple Thermal Analysis Methodologies.

Large strides have been made in designing an ever-increasing set of modern organic materials of high functionality and thus, often, of high complexity, including semiconducting polymers, organic ferroelectrics, light-emitting small molecules, and beyond. Here, we review how broadly applied thermal analysis methodologies, especially differential scanning calorimetry, can be utilized to provide unique information on the assembly and solid-state structure of this extensive class of materials, as well as the phase behavior of intrinsically intricate multicomponent systems. Indeed, highly relevant insights can be gained that are useful, e.g., for further materials-discovery activities and the establishment of reliable processing protocols, in particular if combined with X-ray diffraction techniques, spectroscopic tools, and scanning electron microscopy enabled by vapor-phase infiltration staining. We, hence, illustrate that insights far richer than simple melting point- and glass-transition identification can be obtained with differential scanning calorimetry, rendering it a critical methodology to understand complex matter, including functional macromolecules and blends.

Polymerization-Mediated Through-Space Charge Transfer: An Emerging Strategy for Light-Emitting Materials.

Through-space charge transfer (TSCT) has attracted increasing attention owing to its great potential in designing efficient light-emitting molecules and polymers. Complementary to through-bond charge transfer and Förster resonance energy transfer, TSCT offers an alternative approach for the manipulation of molecular fluorescence. Recently, the synergy between TSCT and polymer systems through polymerization-mediated charge transfer has fostered the advancements of innovative light-emitting functional materials featuring thermally activated delayed fluorescence and/or aggregation-induced emission. This perspective highlights the significant progress in tailoring emission properties through structural engineering of donor and acceptor groups within polymeric systems, leveraging the TSCT mechanism. This strategy has transcended the limitations of traditional charge transfer systems with its tolerance to extended donor-acceptor distance, paving the way for novel applications beyond organic light-emitting diodes. The discussion concludes with a forward-looking analysis of potential future research trajectories in the field of polymerization-mediated charge transfer for developing next-generation light-emitting materials.

High efficiency double light-emitting layer sky blue phosphor organic light-emitting diode with slow emission efficiency attenuation

In this study, by doping the iridium (III) double ((4,6-difluorobenzene) -pyridine-N, C2’Pyridinformate (FIrpic) into 4,4′, 4″ three (carbazole) trioxilamine (TcTa) and 9 (4 tert-butyl-benzene) −3,6 double (triphenylsilyl) -9H carbazole (CzSi) layers as light emitting layers (EMLs) to achieve sky blue phosphor organic electroluminescence (EL) devices with very low efficiency roll-off. The dependence of the EL performance on the doping concentration of the light-emitting molecules and the different EML thicknesses are studied in detail. Experimental data show that the thin-film-doped TcTa layer is very important for the efficiency of the device. Finally, the optimal device achieves extremely high power efficiency, current efficiency, and external quantum efficiency (EQE), reaching 74.82 lm/W, 66.68 cd/A, and 31.9 %, respectively. At a certain luminance of 2000 cd/m2 (3.4 V), the same device retained power efficiency with current efficiency and external quantum efficiency of 57.71 lm/W, 62.46 cd/A and 29.3 %, respectively, based on theoretical discussion, the improved EL efficiency was attributed to the energy levels of the host and luminescent molecules, which helps to balance the charge carrier in the emitter molecule distribution and expand the recombination region.

Role of Spin Polarization and Dynamic Correlation in Singlet-Triplet Gap Inversion of Heptazine Derivatives.

The new generation of proposed light-emitting molecules for organic light-emitting diodes (OLEDs) has raised considerable research interest due to its exceptional feature─a negative singlet-triplet (ST) gap violating Hund's multiplicity rule in the excited S1 and T1 states. We investigate the role of spin polarization in the mechanism of ST gap inversion. Spin polarization is associated with doubly excited determinants of certain types, whose presence in the wave function expansion favors the energy of the singlet state more than that of the triplet. Using a perturbation theory-based model for spin polarization, we propose a simple descriptor for prescreening of candidate molecules with negative ST gaps and prove its usefulness for heptazine-type molecules. Numerical results show that the quantitative effect of spin polarization decreases linearly with the increasing highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) exchange integral. Comparison of single- and multireference coupled-cluster predictions of ST gaps shows that the former methods provide good accuracy by correctly balancing the effects of doubly excited determinants and dynamic correlation. We also show that accurate ST gaps may be obtained using a complete active space model supplemented with dynamic correlation from multireference adiabatic connection theory.

Diverse Synthetic Transformations Using 4-Bromo-3,3,4,4-tetrafluorobut-1-ene and Its Applications in the Preparation of CF2 CF2 -Containing Sugars, Liquid Crystals, and Light-Emitting Materials.

Organic molecules with fluoroalkylene scaffolds, especially a tetrafluoroethylene (CF2 CF2 ) moiety, in their molecular structures exhibit unique biological activities, or can be applied to functional materials such as liquid crystals and light-emitting materials. Although several methods for the syntheses of CF2 CF2 -containing organic molecules have been reported to date, they have been limited to methods using explosives and fluorinating agents. Therefore, there is an urgent need to develop simple and efficient approaches to synthesize CF2 CF2 -containing organic molecules from readily available fluorinated substrates using carbon-carbon bond formation reactions. This personal account summarizes the simple and efficient transformation of functional groups at both ends of 4-bromo-3,3,4,4-tetrafluorobut-1-ene and discusses its synthetic applications to biologically active fluorinated sugars and functional materials, such as liquid crystals and light-emitting molecules.

Wavelength-tunable organic semiconductor lasers based on elastic distributed feedback gratings

Wavelength-tunable organic semiconductor lasers based on mechanically stretchable polydimethylsiloxane (PDMS) gratings were developed. The intrinsic stretchability of PDMS was explored to modulate the period of the distributed feedback gratings for fine tuning the lasing wavelength. Notably, elastic lasers based on three typical light-emitting molecules show comparable lasing threshold values analogous to rigid devices and a continuous wavelength tunability of about 10 nm by mechanical stretching. In addition, the stretchability provides a simple solution for dynamically tuning the lasing wavelength in a spectral range that is challenging to achieve for inorganic counterparts. Our work has provided a simple and efficient method of fabricating tunable organic lasers that depend on stretchable distributed feedback gratings, demonstrating a significant step in the advancement of flexible organic optoelectronic devices.

A comprehensive model of nitrogen-free ordered carbon quantum dots

We propose and demonstrate a novel range of models to accurately determine the optical properties of nitrogen-free carbon quantum dots (CQDs) with ordered graphene layered structures. We confirm the results of our models against the full range of experimental results for CQDs available from an extensive review of the literature. The models can be equally applied to CQDs with varied sizes and with different oxygen contents in the basal planes of the constituent graphenic sheets. We demonstrate that the experimentally observed blue fluorescent emission of nitrogen-free CQDs can be associated with either small oxidised areas on the periphery of the graphenic sheets, or with sub-nanometre non-functionalised islands of sp2-hybridised carbon with high symmetry confined in the centres of oxidised graphene sheets. Larger and/or less symmetric non-functionalised regions in the centre of functionalised graphene sheet are found to be sources of green and even red fluorescent emission from nitrogen-free CQDs. We also demonstrate an approach to simplify the modelling of the discussed sp2-islands by substitution with equivalent strained polycyclic aromatic hydrocarbons. Additionally, we show that the bandgaps (and photoluminescence) of CQDs are not dependent on either out-of-plane corrugation of the graphene sheet or the spacing between sp2-islands. Advantageously, our proposed models show that there is no need to involve light-emitting polycyclic aromatic molecules (nanographenes) with arbitrary structures grafted to the particle periphery to explain the plethora of optical phenomena observed for CQDs across the full range of experimental works.

Gold(i)-containing light-emitting molecules with an inverted singlet-triplet gap.

Delayed fluorescence from molecules with an inverted singlet-triplet gap (DFIST) is the consequence of the unusual reverse order of the lowest excited singlet (S1) and triplet (T1) states of thermally activated delayed fluorescence (TADF) emitters. Heptazine (1,3,4,6,7,9,9b-heptaazaphenalene) derivatives have an inverted singlet-triplet gap thanks to the combination of multiple resonance (MR) effects and a significant double excitation character. Here, we study computationally the effect of gold(i) metalation and coordination on the optical properties of heptazine (molecule 4) and the phosphine-functionalized 2,5,8-tris(dimethylphosphino)heptazine derivatives (molecules 1-3). Ab initio calculations at the approximate second-order coupled cluster (CC2) and extended multiconfigurational quasi degenerate perturbation theory at the second order (XMC-QDPT2) levels show that molecules 1-4 have an inverted singlet-triplet gap due to the alternating spatial localization of the electron and hole of the exciton in the heptazine core. A non-vanishing one-electron spin-orbit coupling operator matrix element between T1 and and a fast S1 ← T1 intersystem crossing rate constant (k ISC) calculated at the XMC-QDPT2(12,12) level of theory for molecule 4 suggest that this new family of complexes may be the first organometallic DFIST emitters reported.

Investigating the influence of substituent groups in TTM based radicals for the excitation process: a theoretical study.

Tri-(2,4,6-trichlorophenyl)methyl (TTM) based radicals can be promising in providing relatively high fluorescence quantum efficiency. In this study, we have evaluated the photoluminescence properties of a series of TTM-based radicals by means of DFT and TD-DFT methods. The optimized structures of the ground states (D0) and the first excited states (D1) of all the radicals are calculated and the computed emission bands are comparable with previous experimental results. knr is determined from transition dipole moments (μ12) and the energy gaps between D0 and D1 (ΔE), both of which can be regulated by the conjugated structures from the substituent groups. knr was derived from the mode-averaging method and is consistent with the experimental results. Factors influencing kr and knr, including the potential energy differences (ΔG0), the vibrational reorganization energies (λ) and the electron coupling term (Hab), are discussed. By comparing kr and knr in solvents with different polarities (cyclohexane, toluene, and chloroform), TTM based radicals in cyclohexane exhibit the most promising fluorescence efficiencies. Besides, two substituted radicals, namely 2Br-TTM-3PCz and 2F-TTM-3PCz, have been fabricated. The results show that fluorine atoms are able to increase ΔG0 and a considerably small knr has been predicted. We expect that our calculation can benefit the design of light-emitting molecules in further experiments.

Efficient organic deep-red to near-infrared light emitters based on boron difluoride curcuminoid derivatives

Organic light-emitting materials in the near-infrared (NIR) region are important for lightweight and wearable medical and military device applications. However, there has been little development of highly efficient NIR light-emitting materials made of purely organic small molecules. This paper introduces tBuPZ and PZ, two novel deep-red to NIR light-emitting curcuminoid boron difluoride derivatives with phenothiazine moiety, to demonstrate organic light-emitting diodes with a maximum external quantum efficiency of 4.11% and 3.92%, respectively, and electroluminescence at 618 nm, with a shoulder peak at 673 nm. By analyzing the donor characteristics of di-tert-butyl substitution, the correlations between electron-donating strength, the emission mechanism, and quantum efficiency were investigated. This study presents a methodology for the design of low toxicity, dye-derived, purely organic NIR light-emitting molecules.

Nanomaterial-Embedded DNA Films on 2D Frames.

Recently, 3D printing has provided opportunities for designing complex structures with ease. These printed structures can serve as molds for complex materials such as DNA and cetyltrimethylammonium chloride (CTMA)-modified DNA that have easily tunable functionalities via the embedding of various nanomaterials such as ions, nanoparticles, fluorophores, and proteins. Herein, we develop a simple and efficient method for constructing DNA flat and curved films containing water-soluble/thermochromatic dyes and di/trivalent ions and CTMA-modified DNA films embedded with organic light-emitting molecules (OLEM) with the aid of 2D/3D frames made by a 3D printer. We study the Raman spectra, current, and resistance of Cu2+-doped and Tb3+-doped DNA films and the photoluminescence of OLEM-embedded CTMA-modified DNA films to better understand the optoelectric characteristics of the samples. Compared to pristine DNA, ion-doped DNA films show noticeable variation of Raman peak intensities, which might be due to the interaction between the ion and phosphate backbone of DNA and the intercalation of ions in DNA base pairs. As expected, ion-doped DNA films show an increase of current with an increase in bias voltage. Because of the presence of metallic ions, DNA films with embedded ions showed relatively larger current than pristine DNA. The photoluminescent emission peaks of CTMA-modified DNA films with OLEMRed, OLEMGreen, and OLEMBlue were obtained at the wavelengths of 610, 515, and 469 nm, respectively. Finally, CIE color coordinates produced from CTMA-modified DNA films with different OLEM color types were plotted in color space. It may be feasible to produce multilayered DNA films as well. If so, multilayered DNA films embedded with different color dyes, ions, fluorescent materials, nanoparticles, proteins, and drug molecules could be used to realize multifunctional physical devices such as energy harvesting and chemo-bio sensors in the near future.

On the origin of the inverted singlet-triplet gap of the 5th generation light-emitting molecules.

Excitation energies of the lowest singlet and triplet state of molecules whose first excited singlet state lies energetically below the first triplet state have been studied computationally at (time-dependent) density functional theory, coupled-cluster, and second-order multiconfiguration perturbation theory levels. The calculations at the ab initio levels show that the singlet-triplet gap is inverted as compared to the one expected from Hund's rule, whereas all density functionals yield the triplet state as the lowest excited state. Double excitations responsible for the inverted singlet-triplet gap have been identified. Employing the spin-flip and ΔSCF methods, singlet-triplet inversion was obtained at the density functional theory level for some of the studied molecules.

N-Phenylcarbazole substituted bis(hexylthiophen-2-yl)-benzothiadiazoles as deep red emitters for hole-transporting layer free solution-processed OLEDs

Two structural isomers of donor-π-acceptor-π-donor (D-π-A-π-D) type red light-emitting molecules (C3TBz and C4TBz), comprising N-phenylcarbazole as a donor, 2,1,3-benzothiadiazole as an acceptor, and either 3-hexylthiophene or 4-hexylthiophene as π-linkages, respectively, were designed and synthesized as hole-transporting emissive materials for OLEDs. C3TBz and C4TBz were chemically characterized, and their photoelectric properties were investigated by spectroscopy, electrochemical and theoretical studies. They showed strong D-A characteristics with intense deep red fluorescence in solutions, decent hole-transporting ability, good thermal and electrochemical stabilities. Both materials were successfully employed as emitters in the solution-processed double-layered OLEDs, which resulted in a pure red emission with promising device performance. Notably, the C3TBz-based device reached the best EL results with a maximum brightness of 2557 cd m−2, a maximum EQE of 3.08%, a maximum luminance efficiency of 4.87 cd A−1, and a low turn-on voltage of 3.2 V.

Acridone and acridinium constructs with red-shifted emission

Acridinium 9-carboxylic acid derivatives have been extensively used as chemiluminescent labels in diagnostic assays. Triggering acridinium with basic hydrogen peroxide produces a highly strained dioxetanone intermediate, which converts into an acridone in an electronically excited state and emits light at 420–440 nm. Here, we introduce a novel acridinium-fluorescein construct emitting at 530 nm, in which fluorescein is covalently attached to the acridinium N-10 nitrogen via a propyl sulfonamide linker. To characterize the spectral properties of the acridinium-fluorescein chemiluminophores, we synthesized the analogous acridone-fluorescein constructs. Both acridinium and acridone were linked to either 5- or 6-carboxyfluorescein and independently synthesized as individual structural isomers. Using fluorescent acridone-fluorophore tandems, we investigated and optimized the diluent composition to prevent dye aggregation. As monomolecular species, the acridone isomers demonstrated similar absorption, excitation, and emission spectra, as well as the expected fluorescence lifetimes and molecular brightness. Chemical triggering of acridinium-fluorescein tandems, as well as direct excitation of their acridone-fluorescein analogs, resulted in a nearly complete energy transfer from acridone to fluorescein. Acridone-based dyes can be studied with steady-state spectroscopy. Thus, they will serve as useful tools for structure and solvent optimizations, as well as for studying chemiluminescent energy transfer mechanisms in related acridinium-fluorophore tandems. Direct investigations of the light-emitting molecules generated in the acridinium chemiluminescent reaction empower further development of chemiluminescent labels with red-shifted emission. As illustrated by the two-color HIV model immunoassay, such labels can find immediate applications for multicolor detection in clinical diagnostic assays.

Aromatic Electrophilic Directing for Fluorescence and Room-Temperature Phosphorescence Modulation.

The ability to modulate luminescence is crucial for organic light-emitting molecules. However, the correlation between molecular structure and emission is not always obvious and systematic. Here, using a well-established empirical rule on electrophilic substitution involving directing groups in organic chemistry, we present a model system, where two luminophores are covalently linked to benzene ortho, meta, and para to each other, to demonstrate that the rule can also be useful in predicting the fluorescence and phosphorescence behaviors of these disubstituted benzene molecules. The benzene ring works as a "molecular wire" that transduces electron density when the two luminophores form ortho- and para-isomers, while little to no transduction can be noted for the meta-isomer, based on well-established organic chemistry. We anticipate that many more "textbook examples" of electronic directing in organic chemistry can be used for systematic modulation of molecular fluorescence and room-temperature phosphorescence.

Recent Advances in Two-Photon AIEgens and Their Application in Biological Systems.

Two-photon fluorescence imaging technology has the advantages of high light stability, little light damage, and high spatiotemporal resolution, which make it a powerful biological analysis method. However, due to the high concentration or aggregation state of traditional organic light-emitting molecules, the fluorescence intensity is easily reduced or disappears completely, and is not conducive to optimal application. The concept of aggregation-induced emission (AIE) provides a solution to the problem of aggregation-induced luminescence quenching (ACQ), and realizes the high fluorescence quantum yield of luminescent molecules in the aggregation state. In addition, two-photon absorption properties can readily be improved just by increasing the loading content of AIE fluorogen (AIEgen). Therefore, the design and preparation of two-photon fluorescence probes based on AIEgen to achieve high-efficiency fluorescence imaging in vitro/in vivo has become a major research hotspot. This review aims to summarize representative two-photon AIEgens based on triphenylamine, tetraphenylethene, quinoline, naphthalene and other new structures from the past five years, and discuss their great potential in bioimaging applications.