Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties.

The racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational-stability issues to the application of this class of compounds. Achieving chiral organic compounds without the risk of racemization is fascinating, but it is challenging due to a lack of strategies. Here, we reveal the cove-regions bridging strategy for achieving persistently chiral multi-helicenes (incapable of racemization), based on the synthesized proof-of-concept double hetero[4]helicenes featuring macrocycle structures with a small 3D cavity. Additionally, we demonstrate that the strategy is also effective in tuning the electronic structures of multi-helicenes, resulting in a conversion from luminescence silence into thermally activated delayed fluorescence (TADF) for the present system. Furthermore, red circularly polarized TADF based on small double [4]helicene systems is achieved for the first time using this strategy. The disclosed cove-regions bridging strategy provides an opportunity to modulate the electronic structures and luminescent properties of multi-helicenes without concern for racemization, thus significantly enhancing the structural and property diversity of multi-helicenes for various applications.

Carbonyl- and Nitrogen-Embedded Multi-Resonance Emitter with Ultra-Pure Green Emission and High Electroluminescence Efficiencies.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with narrow emission spectra have garnered significant attention in future organic light-emitting diode (OLED) displays. However, current C=O/N-embedded MR-TADF systems still lack satisfactory performance in terms of electroluminescence bandwidths and external quantum efficiencies (EQEs). In this study, a C=O/N-embedded green MR-TADF emitter, featuring two acridone units incorporated in a sterically protected 11-ring fused core skeleton, is successfully synthesized through finely controlling the reaction selectivity. The superior combination of multiple intramolecular fusion and steric wrapping strategies in the design of the emitter not only imparts an extremely narrow emission spectrum and a high fluorescence quantum yield to the emitter but also mitigates aggregation-induced spectral broadening and fluorescence quenching. Therefore, the emitter exhibits leading green OLED performance among C=O/N-based MR-TADF systems, achieving an EQE of up to 37.2 %, a full width at half maximum of merely 0.11 eV (24 nm), and a Commission Internationale de l'Éclairage coordinate of (0.20, 0.73). This study marks a significant advance in the realization of ideal C=O/N-based MR-TADF emitters and holds profound implications for the design and synthesis of other MR-TADF systems.

Toward Narrowband and Efficient Blue Fluophosphors by Locking the Stretching Vibration of Indolocarbazole Skeletons.

Developing efficient and color-saturated deep-blue emitting molecules with small Commission Internationale de L'Eclairage (CIE) y values is challenging and has great potential for wide-color gamut displays. Herein, we introduce an intramolecular locking strategy to restrain molecular stretching vibrations of the emission spectral broadening. By cyclizing rigid fluorenes and connecting electron-donating groups to the indolo[3,2,1-jk]-indolo[1',2',3':1,7]indolo[2,3-b]carbazole (DIDCz) framework, the in-plane swing of peripheral bonds and stretching vibrations of the indolocarbazole skeleton are restricted due to an increased steric hindrance from cyclized groups and diphenylamine auxochromophores. As a result, reorganization energies at the high-frequency region (1300-1800 cm-1) are reduced, realizing pure blue emission with a small full-width-at-half-maximum (FWHM) of 30 nm by suppressing shoulder peaks of polycyclic aromatic hydrocarbon (PAH) frameworks. The fabricated bottom-emitting organic light-emitting diode (OLED) exhibits an efficient external quantum efficiency (EQE) of 7.34% and deep-blue coordinates of (0.140, 0.105) at a high brightness of 1000 cd/m2. The FWHM of the electroluminescent spectrum is only 32 nm, which is one of the narrowest electroluminescent emissions among the reported intramolecular charge transfer fluophosphors. Our current findings provide a new molecular design strategy to conceive efficient and narrowband emitters with small reorganization energies.

Donor-Acceptor Type of Fused-Ring Thermally Activated Delayed Fluorescence Compounds Constructed through an Oxygen-Containing Six-Membered Ring.

Nowadays, thermally activated delayed fluorescence (TADF) compounds with a fused-ring core skeleton are getting increasing research interest because of their use in high-performance organic light-emitting diodes (OLEDs). In this study, TADF compounds featuring a D-A-type fused-ring core skeleton are developed. The challenging compatibility of a planarized D-A arrangement and the TADF property is achieved through linking the D and A moieties with two oxygen atoms within a six-membered ring. Compared with a single-oxygen analogue possessing a flexible skeleton and a twisted D-A arrangement, these fused-ring compounds with higher skeleton rigidity show higher photoluminescence quantum yields and narrower emission spectra in toluene and in doped thin films. Their electroluminescent devices achieve high external quantum efficiencies (up to 19.4%), suggesting the potential of rarely achieved D-A-type fused-ring TADF systems to serve as high-performance emitters of OLEDs.

A TADF Emitter Featuring Linearly Arranged Spiro-Donor and Spiro-Acceptor Groups: Efficient Nondoped and Doped Deep-Blue OLEDs with CIEy <0.1.

Reported herein is a molecular design strategy of deep-blue emitters for resolving the lack of highly efficient deep-blue organic light-emitting diodes (OLEDs) featuring CIEy (Commission Internationale de l'Eclairage) color coordinates matching the display requirements (<0.1). The strategy is to combine weak spiro-donor and spiro-acceptor groups into a linear donor-π-acceptor type of thermally-activated delayed fluorescence molecule through a sterically bulky π-spacer. The strategy endows an emitter with deep-blue emission, a narrower emission bandwidth (51 nm in toluene), a high photoluminescence quantum yield (0.95 in toluene), weak concentration quenching, and efficient triplet-exciton utilization, which are all attractive characteristics for emitters of deep-blue OLEDs with lower CIEy coordinates. Owing to the rational design, the emitter has realized not only highly efficient doped deep-blue OLEDs with external quantum efficiencies (EQEs) up to 25.4 % and CIEy less than 0.1 but also so far the most efficient nondoped deep-blue OLED (EQE up to 22.5 %) with CIEy less than 0.1.

Self-Waveguide Single-Benzene Organic Crystal with Ultralow-Temperature Elasticity as a Potential Flexible Material.

With the increasing popularity and burgeoning progress of space technology, the development of ultralow-temperature flexible functional materials is a great challenge. Herein, we report a highly emissive organic crystal combining ultralow-temperature elasticity and self-waveguide properties (when a crystal is excited, it emits light from itself, which travels through the crystal to the other end) based on a simple single-benzene emitter. This crystal displayed excellent elastic bending ability in liquid nitrogen (LN). Preliminary experiments on optical waveguiding in the bent crystal demonstrated that the light generated by the crystal itself could be confined and propagated within the crystal body between 170 and -196 °C. These results not only suggest a guideline for designing functional organic crystals with ultralow-temperature elasticity but also expand the application region of flexible materials to extreme environments, such as space technology.

A Flexible Organic Single Crystal with Plastic-Twisting and Elastic-Bending Capabilities and Polarization-Rotation Function.

Flexible organic single crystals capable of plastic or elastic deformations have a variety of potential applications. Although the integration of plasticity and elasticity in a crystal is theoretically possible and it may cause rich and complex deformations which are highly demanded for potential applications, the integration is hard to realize in practice. Here, we show that through utilizing different modes of external forces for influencing molecular packing in different crystallographic directions, plastic helical twisting and elastic bending can both be achieved for a crystal, and they can even be realized simultaneously. Detailed crystallographic analyses and contrast experiments disclose the mechanisms behind these two kinds of distinct deformations and their mutual compatibility. Based on the plastically twistable nature of the crystal, a new application field of flexible organic single crystals, namely polarization rotators, is successfully opened up.

Achieving High-Performance Pure-Red Electrophosphorescent Iridium(III) Complexes Based on Optimizing Ancillary Ligands.

Two new iridium(III) complexes were synthesized by introducing two trifluoromethyl groups into an ancillary ligand to develop pure-red emitters for organic light-emitting diodes (OLEDs). The electron-donating ability of the ancillary ligands is suppressed, owing to the electron-withdrawing nature of trifluoromethyl groups, which can reduce the HOMO energy levels compared with those of compounds without trifluoromethyl groups. However, the introduction of trifluoromethyl groups into the ancillary ligand has little impact on the LUMO energy levels. Therefore, a well-tuned, pure-red, excited-state energy was achieved by regulating the relative energy level between the HOMO and LUMO. OLEDs with these complexes as emitters showed high external quantum efficiencies (EQEs) of 26 % and realized high EQEs of about 25 % and fairly low driving voltages of 3.3-3.6 V for practical luminance of 1000 cd m-2 , as well as excellent Commission Internationale de L'Eclairage (CIE) coordinates of (0.66, 0.33) and (0.67, 0.33); thus, this demonstrates the successful molecular design strategy by modifying the electron-donating ability of ancillary ligand.

An Organic Crystal with High Elasticity at an Ultra-Low Temperature (77†K) and Shapeability at High Temperatures.

Organic single crystals with elastic bending capability and potential applications in flexible devices and sensors have been elucidated. Exploring the temperature compatibility of elasticity is essential for defining application boundaries of elastic materials. However, related studies have rarely been reported for elastic organic crystals. Now, an organic crystal displays elasticity even in liquid nitrogen (77 K). The elasticity can be maintained below ca. 150 °C. At higher temperatures, the heat setting property enables us to make various shapes of crystalline fibers based on this single kind of crystal. Through detailed crystallographic analyses and contrast experiments, the mechanisms behind the unusual low-temperature elasticity and high-temperature heat setting are disclosed.

Polymorph-Dependent Luminescence Response to Acid Vapors and Its Application in Safety Protection of File Information.

A Schiff base, (E)-1-(phenylimino)methyl-2-hydroxylnaphthalene (PIHN), was found to form both nonluminescent and luminescent polymorphs. A unique luminescence "turn on" behavior was observed when the nonluminescent polymorph was fumed with the vapor of aliphatic acids with two or three carbons in the main chain, while the luminescent polymorphs almost did not change the emission color under the same condition. As we know, this is the first report on polymorph-dependent acid response which discloses the influence of crystalline phase on acid-responsive behavior. The formation of hydrogen bonds between PIHN and aliphatic acid is proposed to be the reason for the responsive behavior of the nonemissive polymorph, and such a mechanism is different from the common protonation mechanism. A novel safety protection method of file information has been developed based on the polymorph-dependent luminescence response of PIHN. In addition, we disclose that a crystalline form could show multiple responsive behaviors toward different acids, which benefits the further design of novel acid sensors, such as the sensors that can qualitatively analyze the species of the acid source in an acidic environment.

The Effect of Branching on the One- and Two-Photon Absorption, Cell Viability, and Localization of Cationic Triarylborane Chromophores with Dipolar versus Octupolar Charge Distributions for Cellular Imaging.

Two different chromophores, namely a dipolar and an octupolar system, were prepared and their linear and nonlinear optical properties as well as their bioimaging capabilities were compared. Both contain triphenylamine as the donor and a triarylborane as the acceptor, the latter modified with cationic trimethylammonio groups to provide solubility in aqueous media. The octupolar system exhibits a much higher two-photon brightness, and also better cell viability and enhanced selectivity for lysosomes compared with the dipolar chromophore. Furthermore, both dyes were applied in two-photon excited fluorescence (TPEF) live-cell imaging.

Highly Elastic Organic Crystals for Flexible Optical Waveguides.

The study of elastic organic single crystals (EOSCs) has emerged as a cutting-edge research of crystal engineering. Although a few EOSCs have been reported recently, those suitable for optical/optoelectronic applications have not been realized. Here, we report an elastic crystal of a Schiff base, (E)-1-(4-(dimethylamino)phenyl)iminomethyl-2-hydroxyl-naphthalene. The crystal is highly bendable under external stress and able to regain immediately its original straight shape when the stress is released. It displays bright orange-red emission with a high fluorescence quantum yield of 0.43. Intriguingly, it can serve as a low-loss optical waveguide even at the highly bent state. Our result highlights the feature and utility of "elasticity" of organic crystals.

2-(2-Hydroxyphenyl)imidazole-based four-coordinate organoboron compounds with efficient deep blue photoluminescence and electroluminescence.

Two new four-coordinate organoboron compounds with 2-(2-hydroxyphenyl)imidazole derivatives as the chelating ligands have been synthesized. They possess high thermal stability and are able to form an amorphous glass state. Crystallographic analyses indicate that the differences in ligand structure cause the change of ππ stacking character. The CH2Cl2 solutions and thin films of these compounds display bright blue emission, and these compounds have appropriate HOMO and LUMO energy levels for carrier injection in OLEDs. By utilizing the good thermal and luminescent properties, as well as the proper frontier orbital energy levels, bright non-doped OLEDs with a simple structure have been realized. Notably, these simple devices show deep blue electroluminescence with the Commission Internationale de l'Éclairage (CIE) coordinate of ca. (0.16, 0.08), which is close to the CIE coordinate of (0.14, 0.08) for standard blue defined by the National Television System Committee. In addition, one of the devices exhibits good performance, showing brightness, current efficiency, power efficiency and external quantum efficiency up to 2692 cd m-2, 2.50 cd A-1, 1.81 lm W-1 and 3.63%, respectively. This study not only provides good deep-blue emitting OLED materials that are rarely achieved by using four-coordinate organoboron compounds, but also allows a deeper understanding of the structure-property relationship of 2-(2-hydroxyphenyl)imidazole-based boron complexes, which benefits the further structural design of this type of material.

Single-Molecule-based White-Light Emissive Organic Solids with Molecular-Packing-Dependent Thermally Activated Delayed Fluorescence.

White-light-emitting single molecules have attracted broad attention because of their great potential for use in flat-panel displays and future light sources. We report a unique molecule of 3-(diphenylamino)-9H-xanthen-9-one (3-DPH-XO), which was found to exhibit bright white-light emission in the solid state caused by the spontaneous formation of a mixture with different polymorphs. Single-crystal analyses demonstrate that noncovalent interactions (such as π···π stacking, hydrogen bonding, and C-H···π interactions) induce different stacking arrangements (polymorphs A, B, and C) with different photophysical properties in a molecular solid. In addition, crystals B and C with the acceptor···acceptor stacking feature show the thermally activated delayed fluorescence (TADF) characteristics, indicating that appropriate noncovalent interactions could enhance the reverse intersystem crossing process and consequently lead to delayed fluorescence. This discovery provides an effective strategy for the design of new white-light-emitting single molecules as well as TADF materials.

Geometric Shape Regulation and Noncovalent Synthesis of One-Dimensional Organic Luminescent Nano-/Micro-Materials.

Noncovalent synthesis of one-dimensional (1D) organic nano-/micro-materials with controllable geometric shapes or morphologies and special luminescent and electronic properties is one of the greatest challenges in modern chemistry and material science. Control of noncovalent interactions is fundamental for realizing desired 1D structures and crucial for understanding the functions of these interactions. Here, a series of thiophene-fused phenazines composed of a halogen-substituted π-conjugated plate and a pair of flexible side chains is presented, which displays halogen-dependent 1D self-assemblies. Luminescent 1D twisted wires, straight rods, and zigzag wires, respectively, can be generated in sequence when the halogen atoms are varied from the lightest F to the heaviest I. It was demonstrated that halogen-dependent anisotropic noncovalent interactions and mirror-symmetrical crystallization dominated the 1D-assembly behaviors of this class of molecules. The methodology developed in this study provides a potential strategy for constructing 1D organic materials with unique optoelectronic functions.

Water-Soluble Triarylborane Chromophores for One- and Two-Photon Excited Fluorescence Imaging of Mitochondria in Cells.

Three water-soluble tetracationic quadrupolar chromophores comprising two three-coordinate boron π-acceptor groups bridged by thiophene-containing moieties were synthesised for biological imaging applications. Compound 3 containing the bulkier 5-(3,5-Me2 C6 H2 )-2,2'-(C4 H2 S)2 -5'-(3,5-Me2 C6 H2 ) bridge is stable over a long period of time, exhibits a high fluorescence quantum yield and strong one- and two-photon absorption (TPA), and has a TPA cross section of 268 GM at 800 nm in water. Confocal laser scanning fluorescence microscopy studies in live cells indicated localisation of the chromophore at the mitochondria; moreover, cytotoxicity measurements proved biocompatibility. Thus, chromophore 3 has excellent potential for one- and two-photon-excited fluorescence imaging of mitochondrial function in cells.

Synthesis and fluxional behaviour of novel chloroborole dimers.

The (B-Cl)-chloroboroles 2-chloro-1,3-di(4-R-phenyl)-2,4,5,6-tetra-hydrocyclopenta[c]borole (R = H, Br) undergo a novel dimerisation process in CH2Cl2 solution. The resulting unsymmetric dimers are highly fluxional in solution via reversible enantiomerisation through an intermediate with mirror symmetry. DFT calculations suggest an unusual dimerisation mechanism and provide insight into the dynamics of the dimers.

Large π-Conjugated Quinacridone Derivatives: Syntheses, Characterizations, Emission, and Charge Transport Properties.

Two 11-ring-fused quinacridone derivatives, TTQA and DCNTTQA, have been synthesized by ferric chloride mediated cyclization and Knoevenagel reaction. Replacement of the carbonyl groups (in TTQA) with dicyanoethylene groups (in DCNTTQA) not only red-shifted the emission to the near-infrared region but also led to a nonplanar skeleton that significantly improved the solubility of DCNTTQA. Moreover, dicyanoethylene groups rendered DCNTTQA low-lying HOMO and LUMO levels. DCNTTQA-based solution-processed field-effect transistors showed a hole mobility up to 0.217 cm(2) V(-1) s(-1).

Diboron complexes with bis-spiro structures as high-performance blue emitters for OLEDs.

To construct high-performance organoboron-based blue emitters for electroluminescent (EL) devices, two diboron complexes have been synthesized through the chelation of 2-(1-phenyl-1H-benzo[d]imidazole-2-yl)phenol or 2-(2-pyridyl)phenol ligands with both boron atoms of the 9,10-diboraanthracene group. These complexes exhibit bright blue emissions in solution and in solid films with fluorescence quantum yields over 0.42, which benefit from their bis-spiro structures. In addition, they possess high thermal decomposition (>410 °C) and glass transition (>163 °C) temperatures. Moreover, they are excellent ambipolar transporting materials with high and balanced mobilities (>10(-4) cm(2) V(-1) s(-1)) for holes and electrons. Due to these excellent properties, the EL devices adopting these complexes as non-doped emitting layers emit blue light and exhibit low turn-on voltages (<3.2 V), high luminance (up to 9041 cd m(-2)), as well as high current (up to 7.01 cd A(-1)) and power efficiencies (up to 7.58 lm W(-1)). To the best of our knowledge, these devices are so far the brightest and most efficient blue devices based on four-coordinate organoboron emitters.

Taming the beast: fluoromesityl groups induce a dramatic stability enhancement in boroles.

The electron-deficient pentaarylborole 1-(2',4',6'-tris(trifluoromethyl)phenyl)-2,3,4,5-tetraphenylborole (1) has been synthesised with the long-term aim of developing borole-based optoelectronic materials. The bulky 2,4,6-tris(trifluoromethyl)phenyl (FMes) group on the boron atom of 1 significantly improves (>600 times) its air stability relative to its mesityl analogue. Moreover, 1 shows good thermal stability without undergoing the dimerisation or isomerisation reactions reported for some other boroles. A triarylborole analogue (2), belonging to a new class of borole with the 3- and 4-positions of the BC4 ring linked by a -(CH2)3- group, has also been synthesised to elucidate the influence of carbon-bonded substituents on the stability of boroles. Both boroles were prepared through the reaction of Li[FMesBF3] and divinyldilithium reagents, a new and general method for borole syntheses. Compound 2 was found to isomerise through a [1,3]-H shift and double-bond rearrangement to an s-trans-butadienylborane species under highly basic (NaOH) conditions. The increased steric crowding at the boron centre through incorporation of the FMes group does not preclude binding of Lewis bases to either 1 or 2, as demonstrated by their fully reversible binding of pyridine. Interestingly, 1 exhibits a blue-shifted absorption spectrum, as compared with its mesityl analogue, a result contrary to previous understanding of the influence of substituent electronics on the absorption spectra of boroles. Most importantly, these boroles exhibit much greater air-stability than previously reported analogues without sacrificing the strong electron-accepting ability that makes boroles so attractive; indeed, 1 and 2 have very low reduction potentials of -1.52 and -1.69 eV vs. Fc/Fc+, respectively.