Luminescence Color‐Tuning through Polymorph Doping: Preparation of a White‐Emitting Solid from a Single Gold(I)–Isocyanide Complex by Simple Precipitation

We report the luminescent color tuning of a new complex, 2‐benzothiophenyl(4‐methoxyphenyl isocyanide)gold(I) ( 1 ), by using a new “polymorph doping” approach. The slow crystallization of the complex 1 afforded three different pure polymorphic crystals with blue, green, and orange emission under UV‐light irradiation. The crystal structures of pure polymorphs of 1 were investigated in detail by means of single‐crystal X‐ray analyses. Theoretical calculations based on the single‐crystal structures provided qualitative explanation of the difference in the excited energy‐levels of the three polymorphs of 1 . In sharp contrast, the rapid precipitation of 1 , with the optimized conditions reproducibly afforded homogeneous powder materials showing solid‐state white‐emission with Commission Internationale de l’Éclairage (CIE) 1931 chromaticity coordinates of (0.33, 0.35), which is similar to pure white. New “polymorphic doping” has been revealed to be critical to this white emission through spectroscopic and X‐ray diffraction analyses. The coexistence of the multiple polymorphs of 1 within the homogeneous powder materials and the ideal mixing of multiple luminescent colors gave its white emission accompanied with energy transfer from the predominant green‐emitting polymorph to the minor orange‐emitting polymorph.     

In situ access to white light‐emitting fluorescent polymer nanocomposites via plasma‐ignited frontal polymerization

We describe a facile fabrication of white light‐emitting cadmium sulfide (CdS)‐poly(HEA‐co‐NVK) nanocomposites [2‐hydroxyethyl acrylate (HEA) and N‐vinylcarbazole (NVK)] via plasma‐ignited frontal polymerization (PIFP), a novel and rapid reaction mode of converting monomers into polymers in minutes. Frontal polymerization was initiated by igniting the upper side of the reactant with plasma. Once initiated, no additional energy was required for the polymerization to occur. The chemical functional groups of the as‐prepared nanocomposites were thoroughly investigated using Fourier transform infrared spectra. The dependence of the front velocity and front temperature on the initiator concentration and weight ratios of HEA/NVK was also investigated in detail. Perhaps more interestingly, the white light‐emitting materials synthesized by ingeniously incorporating the compensating colors of yellow emitting from 3‐(trimethoxysilyl)‐1‐propanethiol‐capped CdS nanocrystals and blue emitting from carbazole‐containing polymer were conveniently applied onto a commercial UV light‐emitting diode (LED) to generate white LEDs. The subtle change in the weight ratios of CdS/NVK can significantly impact the color hue. The white light becomes gradually colder with the increase of NVK, but becomes gradually warmer with the increase concentration of CdS nanocrystals. In a broad perspective, these white light‐emitting materials designed by PIFP approach will open a new pathway to develop “QD‐polymer nanocomposite down‐conversion LED” in a fast and efficient way. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Luminescent Platinum(II) Complexes of 1,3‐Bis(N‐alkylbenzimidazol‐ 2′‐yl)benzene‐Type Ligands with Potential Applications in Efficient Organic Light‐Emitting Diodes

A series of luminescent platinum(II) complexes of tridentate 1,3‐bis(N‐alkylbenzimidazol‐2′‐yl)benzene (bzimb) ligands has been synthesized and characterized. One of these platinum(II) complexes has been structurally characterized by X‐ray crystallography. Their electrochemical, electronic absorption, and luminescence properties have been investigated. Computational studies have been performed on this class of complexes to elucidate the origin of their photophysical properties. Some of these complexes have been utilized in the fabrication of organic light‐emitting diodes (OLEDs) by using either vapor deposition or spin‐coating techniques. Chloroplatinum(II)? bzimb complexes that are functionalized at the 5‐position of the aryl ring, [Pt(R‐bzimb)Cl], not only show tunable emission color but also exhibit high current and external quantum efficiencies in OLEDs. Concentration‐dependent dual‐emissive behavior was observed in multilayer OLEDs upon the incorporation of pyrenyl ligand into the Pt(bzimb) system. Devices doped with low concentrations of the complexes gave rise to white‐light emission, thereby representing a unique class of small‐molecule, platinum(II)‐based white OLEDs.     

White‐Light Emission from a Semi‐Conductive Borate‐Stannate

In response to ever‐increasing application requirements in lighting and displays, a tremendous emphasis is being placed on single‐component white‐light emission. Single‐component inorganic borates doped with rare earth metal ions have shown prominent achievements in white‐light emission. The first environmentally friendly defect‐induced white‐light emitting crystalline inorganic borate, Ba₂[Sn(OH)₆][B(OH)₄]₂, has been prepared. Additionally, it is the first borate‐stannate without a Sn?O?B linkage. Notably, Ba₂[Sn(OH)₆][B(OH)₄]₂ shows Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.42, 0.38), an ultrahigh color rendering index (CRI) of 94.1, and an appropriate correlated color temperature (CCT) of 3083 K. Such a promising material will provide a new approach in the development of white‐light emitting applications.     

Intercrossed Carbon Nanorings with Pure Surface States as Low‐Cost and Environment‐Friendly Phosphors for White‐Light‐Emitting Diodes

As an important energy‐saving technique, white‐light‐emitting diodes (W‐LEDs) have been seeking for low‐cost and environment‐friendly substitutes for rare‐earth‐based expensive phosphors or Pd²⁺/Cd²⁺‐based toxic quantum dots (QDs). In this work, precursors and chemical processes were elaborately designed to synthesize intercrossed carbon nanorings (IC‐CNRs) with relatively pure hydroxy surface states for the first time, which enable them to overcome the aggregation‐induced quenching (AIQ) effect, and to emit stable yellow‐orange luminescence in both colloidal and solid states. As a direct benefit of such scarce solid luminescence from carbon nanomaterials, W‐LEDs with color coordinate at (0.28, 0.27), which is close to pure white light (0.33, 0.33), were achieved through using these low‐temperature‐synthesized and toxic ion‐free IC‐CNRs as solid phosphors on blue LED chips. This work demonstrates that the design of surface states plays a crucial role in exploring new functions of fluorescent carbon nanomaterials.     

White‐Light Emission Strategy of a Single Organic Compound with Aggregation‐Induced Emission and Delayed Fluorescence Properties

A novel white‐light‐emitting organic molecule, which consists of carbazolyl‐ and phenothiazinyl‐substituted benzophenone (OPC) and exhibits aggregation‐induced emission‐delayed fluorescence (AIE‐DF) and mechanofluorochromic properties was synthesized. The CIE color coordinates of OPC were directly measured with a non‐doped powder, which presented white‐emission coordinates (0.33, 0.33) at 244 K to 252 K and (0.35, 0.35) at 298 K. The asymmetric donor–acceptor–donor′ (D‐A‐D′) type of OPC exhibits an accurate inherited relationship from dicarbazolyl‐substituted benzophenone (O2C, D‐A‐D) and diphenothiazinyl‐substituted benzophenone (O2P, D′‐A‐D′). By purposefully selecting the two parent molecules, that is, O2C (blue) and O2P (yellow), the white‐light emission of OPC can be achieved in a single molecule. This finding provides a feasible molecular strategy to design new AIE‐DF white‐light‐emitting organic molecules.     

Synthesis of Multifunctional Mn‐Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water‐soluble Mn‐doped CdTe/ZnS core‐shell quantum dots using a proposed ultrasonic assistant method and 3‐mercaptopropionic acid (MPA) as stabilizer is descried. To obtain a high luminescent intensity, post‐preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn‐doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100°C and reflux time 3 h under N₂ atmosphere. While for phosphorescent Mn‐doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100°C and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn‐doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photoluminescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn²⁺ ions in the as‐prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn‐doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron‐hole pairs, attributing to the transition from the triplet state (⁴T₁) to the ground state (⁶A₁) of the Mn²⁺ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn‐doped CdTe/ZnS core‐shell quantum dots.     

Luminous Butterflies: Efficient Exciton Harvesting by Benzophenone Derivatives for Full‐Color Delayed Fluorescence OLEDs

Butterfly‐shaped luminescent benzophenone derivatives with small energy gaps between their singlet and triplet excited states are used to achieve efficient full‐color delayed fluorescence. Organic light‐emitting diodes (OLEDs) with these benzophenone derivatives doped in the emissive layer can generate electroluminescence ranging from blue to orange–red and white, with maximum external quantum efficiencies of up to 14.3 %. Triplet excitons are efficiently harvested through delayed fluorescence channels.     

Synthesis and characterization of novel germanium‐containing poly(p‐phenylenevinylene) derivatives

Novel blue‐emitting germanium‐containing poly(p‐phenylenevinylene) (PPV) derivatives with well‐defined conjugation lengths were synthesized via Wittig‐condensation polymerizations. The polymers can be color‐tuned by the introduction of various chromophores into the PPV‐based polymer backbones. The photoluminescence (PL) spectra of the polymers, GePVK (containing carbazole moieties), GeMEH (containing dialkoxybenzene moieties), and GePTH (containing phenothiazine moieties), were found to exhibit blue, greenish blue, and green emissions, respectively. GePTH produces more red‐shifted emission than GeMEH and GEPVK, resulting in green emission, and the solution and solid state PL spectra of GePVK consist of almost blue emission. The electroluminescence spectra of GeMEH and GePTH contain yellowy green and yellow colors, respectively. Interestingly, GePVK exhibits white emission with CIE coordinates of (0.33, 0.37) due to electroplex emission in the light‐emitting diodes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 979–988, 2008     

A Unique Blend of 2‐Fluorenyl‐2‐anthracene and 2‐Anthryl‐2‐anthracence Showing White Emission and High Charge Mobility

White‐light‐emitting materials with high mobility are necessary for organic white‐light‐emitting transistors, which can be used for self‐driven OLED displays or OLED lighting. In this study, we combined two materials with similar structures—2‐fluorenyl‐2‐anthracene (FlAnt) with blue emission and 2‐anthryl‐2‐anthracence (2A) with greenish‐yellow emission—to fabricate OLED devices, which showed unusual solid‐state white‐light emission with the CIE coordinates (0.33, 0.34) at 10 V. The similar crystal structures ensured that the OTFTs based on mixed FlAnt and 2A showed high mobility of 1.56 cm² V⁻¹ s⁻¹. This simple method provides new insight into the design of high‐performance white‐emitting transistor materials and structures.     

Molecular Topology Tuning of Bipolar Host Materials Composed of Fluorene‐Bridged Benzimidazole and Carbazole for Highly Efficient Electrophosphorescence

Two new molecules, CzFCBI and CzFNBI , have been tailor‐made to serve as bipolar host materials to realize high‐efficiency electrophosphorescent devices. The molecular design is configured with carbazole as the hole‐transporting block and N‐phenylbenzimidazole as the electron‐transporting block hybridized through the saturated bridge center (C9) and meta‐conjugation site (C3) of fluorene, respectively. With structural topology tuning of the connecting manner between N‐phenylbenzimidazole and the fluorene core, the resulting physical properties can be subtly modulated. Bipolar host CzFCBI with a C connectivity between phenylbenzimidazole and the fluorene bridge exhibited extended π conjugation; therefore, a low triplet energy of 2.52 eV was observed, which is insufficient to confine blue phosphorescence. However, the monochromatic devices indicate that the matched energy‐level alignment allows CzFCBI to outperform its N‐connected counterpart CzFNBI while employing other long‐wavelength‐emitting phosphorescent guests. In contrast, the high triplet energy (2.72 eV) of CzFNBI imparted by the N connectivity ensures its utilization as a universal bipolar host for blue‐to‐red phosphors. With a common device configuration, CzFNBI has been utilized to achieve highly efficient and low‐roll‐off devices with external quantum efficiency as high as 14 % blue, 17.8 % green, 16.6 % yellowish‐green, 19.5 % yellow, and 18.6 % red. In addition, by combining yellowish‐green with a sky‐blue emitter and a red emitter, a CzFNBI ‐hosted single‐emitting‐layer all‐phosphor three‐color‐based white electrophosphorescent device was successfully achieved with high efficiencies (18.4 %, 36.3 cd A^?1, 28.3 lm W^?1) and highly stable chromaticity (CIE x=0.43–0.46 and CIE y=0.43) at an applied voltage of 8 to 12 V, and a high color‐rendering index of 91.6.     

Efficient Nondoped Pure Blue Organic Light‐Emitting Diodes Based on an Anthracene and 9,9‐Diphenyl‐9,10‐dihydroacridine Derivative

Organic light‐emitting diodes (OLEDs) have been greatly developed in recent years owing to their abundant advantages for full‐color displays and general‐purpose lightings. Blue emitters not only provide one of the primary colors of the RGB (red, green and blue) display system to reduce the power consumption of OLEDs, but are able able to generate light of all colors, including blue, green, red, and white by energy transfer processes in devices. However, it remains a challenge to achieve high‐performance blue electroluminescence, especially for nondoped devices. In this paper, we report a blue light emitting molecule, DPAC‐AnPCN, which consists of 9,9‐diphenyl‐9,10‐dihydroacridine and p‐benzonitrile substituted anthracene moieties. The asymmetrically decoration on anthracene with different groups on its 9 and 10 positions combines the merits of the respective constructing units and endows DPAC‐AnPCN with pure blue emission, high solid‐state efficiency, good thermal stability and appropriate HOMO and LUMO energy levels. Furthermore, DPAC‐AnPCN can be applied in a nondoped device to effectively reduce the fabrication complexity and cost. The nondoped device exhibits pure blue electroluminescence (EL) locating at 464 nm with CIE coordinates of (0.15, 0.15). Moreover, it maintains high efficiency at relatively high luminescence. The maximum external quantum efficiency (EQE) reaches 6.04 % and still remains 5.31 % at the luminance of 1000 cd m^?2 showing a very small efficiency roll‐off.     

Stimulus‐Triggered Formation of an Anion–Cation Exciplex in Copper(I) Complexes as a Mechanism for Mechanochromic Phosphorescence

The investigation of the mechanisms of mechanochromic luminescence is of fundamental importance for the development of materials for photonic sensors, data storage, and luminescence switches. The structural origin of this phenomenon in phosphorescent molecular systems is rarely known and thus the formulation of structure–property relationships remains challenging. Changes in the M–M interactions have been proposed as the main mechanism with d¹⁰ coinage metal compounds. Herein, we describe a new mechanism—a mechanically induced reversible formation of a cation–anion exciplex based on Cu–F interactions—that leads to highly efficient mechanochromic phosphorescence and unusual large emission shifts from UV‐blue to yellow for Cu^I complexes. The low‐energy luminescence is thermo‐ and vaporesponsive, thus allowing the generation of white light as well as for recovering the original UV‐blue emission.     

Reversible Luminescent Switching in an Organic Cocrystal: Multi‐Stimuli‐Induced Crystal‐to‐Crystal Phase Transformation

A luminescent cocrystal system is reported to undergo crystal‐to‐crystal phase transformation from yellow‐emitting polymorph I to green‐emitting polymorph II, triggered by THF fuming or heating, and the green emission can recover to the initial yellow emission by grinding. The established spectroscopic and crystallographic analyses demonstrate that the phase transition occurred and benefits from the combined effect of similar molecular arrange sequence and unique alteration of intermolecular interactions from halogen/hydrogen bonds in I to π–π stacking in II. Furthermore, I and II exhibit red‐shift emission under hydrostatic pressure. The emission of I and II shows a red‐shift and recovers towards the initial emission upon acid–base fuming. This is a rare example of reversible luminescent switching of cocrystal based upon crystal‐to‐crystal phase transition, and provides an alternative strategy to develop multi‐stimuli responsive materials.     

Thermal or Mechanical Stimuli‐Induced Photoluminescence Color Change of a Molecular Assembly Composed of an Amphiphilic Anthracene Derivative in Water

Molecular assemblies that change photoluminescence color in response to thermal or mechanical stimulation without dissociation into the monomeric states in water are described herein. A dumbbell‐shaped amphiphilic compound forms micellar molecular assemblies in water and exhibits yellow photoluminescence derived from excimer formation of the luminescent core, which contains a 2,6‐diethynylanthracene moiety. Annealing of the aqueous solution induces a photoluminescence color change from yellow to green (λ_{em, max}=558→525 nm). The same photoluminescence color change is also achieved by rubbing the yellow‐photoluminescence‐emitting molecular assemblies adsorbed on glass substrates with cotton wool in water. The observed green photoluminescence is ascribed to micelles that are distinct from the yellow‐photoluminescence‐emitting micelles, on the basis of transmission electron microscopy observations, atomic force microscopy observations, and dynamic light scattering measurements. We examined the relationship between the structure of the molecular assemblies and the photophysical properties of the anthracene derivative in water before and after thermal or mechanical stimulation and concluded that thermal or mechanical stimuli‐induced slight changes of the molecular‐assembled structures in the micelles result in the change in the photoluminescence color from yellow to green in water.     

Luminescence Enhancement based Sensing of L‐Cysteine by Doped Quantum Dots

The interaction of a presynthesized orange emitting Mn²⁺‐doped ZnS quantum dots (QDs) with L‐Cysteine (L?Cys) led to enhance emission intensity (at 596 nm) and quantum yield (QY). Importantly, the Mn²⁺‐doped ZnS QDs exhibited high sensitivity towards L?Cys, with a limit of detection of 0.4±0.02 μM (in the linear range of 3.3–13.3 μM) and high selectivity in presence of interfering amino acids and metal ions. The association constant of L?Cys was determined to be 0.36×10⁵ M^?1. The amplified passivation of the surface of Mn²⁺‐doped ZnS QDs following the incorporation and binding of L?Cys is accounted for the enhancement in their luminescence features. Moreover, the luminescence enhancement‐based detection will bring newer dimension towards sensing application.     

Achieving Pure Deep‐Blue Electroluminescence with CIE y≤0.06 via a Rational Design Approach for Highly Efficient Non‐Doped Solution‐Processed Organic Light‐Emitting Diodes

Deep‐blue fluorescent emitters with Commission Internationale de l'Eclairage (CIE) y≤0.06 are urgently needed for high‐density storage, full‐color displays and solid‐state lighting. However, developing such emitters with high color purity and efficiency in solution‐processable non‐doped organic light‐emitting diodes (OLEDs) remains an important challenge. Here, we present the synthesis of two new deep‐blue fluorescent emitters ( AFpTPI and AFmTPI ) based on 10‐(9,9‐diethyl‐9H‐fluoren‐2‐yl)‐9,9‐dimethyl‐9,10‐dihydroacridine as a core and 1,3‐ and/or 1,4‐phenylene‐linked triphenylimidazole (TPI) analogues for non‐doped solution‐processable OLEDs. Their thermal, photophysical, electrochemical, and device characteristics are explored, and also strongly supported by density functional theory (DFT) study. AFpTPI and AFmTPI exhibit excellent thermal stability (≈450 °C) with high glass transition temperatures (T_g; 141–152 °C) and deep‐blue emission with high quantum yields. Specifically, the solution‐processed non‐doped device with AFpTPI as an emitter exhibits a maximum external quantum efficiency (EQE) of 4.56 % with CIE coordinates of (0.15, 0.06), which exactly matches the European Broadcasting Union (EBU) blue standard. In addition, AFmTPI also displays good efficiency and better color purity (EQE: 3.37 %; CIE (0.15, 0.05)). To the best of our knowledge, the present work is the first report on non‐doped solution‐processable OLEDs with efficiency close to 5 % and CIE y≤0.06.     

High red,green, and blue color purity electroluminescence from MEH‐PPV and polyalkyfluorenes‐based bright white polymer light emitting displays

A series of white polymer light emitting displays (PLEDs) based on a polymer blend of polyalkylfluorenes and poly(2‐methoxy‐5,2′‐ethyl‐hexyloxy‐1,4‐phenylene vinylene) (MEH‐PPV) was developed. MEH‐PPV or red light emitting alkyfluorene copolymer (PFR) was blended with blue light emitting alkyfluorene copolymer (PFB), and MEH‐PPV was blended with both green light emitting alkyfluorene copolymer (PFG) and PFB to generate white light emission PLEDs. Low turn on voltage (2.7 V), high brightness (12,149 nits), high efficiency (4.0 cd/A, 4.0 lm/W), and good color purity (Commission Internationale de L'Eclairage (CIE_x,y) co‐ordinates (0.32, 0.34)) were obtained for the white PLEDs based on the PFB and MEH‐PPV polymer blend. Exciplex formation in the interface between PFR and PFB induced a new green emission peak for these two components based white PLEDs. As a result, strong white emission (4078 nits) was obtained by mixing the red, green, and blue (RGB) three primary colors. High color purity of blue (CIE, x = 0.14, y = 0.08), green (CIE, x = 0.32, y = 0.64) and red (CIE, x = 0.67, y = 0.33) emissions was achieved for white PLEDs combining with dielectric interference color‐filters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 330–341, 2007     

Efficient Non‐doped Blue Fluorescent Organic Light‐Emitting Diodes Based on Anthracene–Triphenylethylene Derivatives

The development of efficient blue materials has been a continuous research topic in the field of organic light‐emitting diodes (OLEDs). In this paper, three aggregation‐induced emission enhancement active blue emitters, PIAnTPE, TPAAnTPE and CzAnTPE, are successfully synthesized by attaching a triphenylethylene unit and phenanthroimidazole/triphenylamine/carbazole moieties to the 9,10‐positions of anthracene, respectively. The three compounds exhibit good thermal stabilities, appropriate for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels and display high photoluminescence quantum yields (PLQYs) of 65, 70 and 46 % in the solid state. Non‐doped blue devices using PIAnTPE, TPAAnTPE and CzAnTPE as the emitting layers show good electroluminescent performances, with the maximum external quantum efficiencies (EQEs) of 4.46, 4.13 and 4.04 %, respectively. More importantly, EQEs of all the three devices can be still retained when the luminescence reaches 1000 cd m^?2, exhibiting quite small efficiency roll‐offs in the non‐doped OLEDs.     

High‐Performance Non‐doped OLEDs with Nearly 100 % Exciton Use and Negligible Efficiency Roll‐Off

Non‐doped organic light‐emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton use are generally unsuitable for non‐doped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation‐induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for non‐doped OLEDs. By grafting 4‐(phenoxazin‐10‐yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Non‐doped OLEDs of these AIDF luminogens exhibit excellent luminance (ca. 100000 cd m^?2), outstanding external quantum efficiencies (21.4–22.6 %), negligible efficiency roll‐off and improved operational stability. To the best of our knowledge, these are the most efficient non‐doped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of non‐doped OLEDs.