Weak Charge Transfer Research Articles

High‐Efficiency and Narrow‐Band Near‐Ultraviolet Emitters with Low CIEy of 0.03 by Incorporating Extra Weak Charge Transfer Channel into Multi‐Resonance Skeleton

AbstractHybridized local and charge‐transfer (HLCT) excited‐state emitters can effectively utilize non‐radiative triplet excitons through high‐lying reverse intersystem crossing (hRISC), but they are mostly limited to the donor‐π‐acceptor type molecules. It is a great challenge to develop high‐performance near‐ultraviolet (NUV) emitters with narrow‐band emission by HLCT due to the large carrier injection barriers and high triplet energy. In this work, by incorporating planar multi‐resonance (MR) skeleton of oxygen‐bridged triphenylborane (BO) and weak electron‐donating unit of tetraphenyl‐silane (TPS), two NUV emitters of tBOSi and tBOSiCz are developed, where an extra weak charge transfer (CT) channel between BO skeleton and peripheral phenyl in TPS is observed to increase CT component and activate hot exciton channel of hRISC. As a result, tBOSi and tBOSiCz show an outstanding narrow‐band NUV emission at 414 nm with a FWHM of about 32 nm in solution‐processed organic light‐emitting diodes (OLEDs), even at a heavy doping ratio. The best NUV electroluminescent properties are further achieved in the optimal tBOSi‐doped OLEDs with a record efficiency of 9.15% and a low CIEy of 0.034. This work provides a profound guidance for developing high‐performance narrow‐band NUV emitters by an extra weak CT channel into MR skeleton to activate HLCT emission.

Physical Mechanism of Nonlinear Spectra in Triangene.

In this work, we theoretically investigate the linear and nonlinear optical absorption properties of open triangulene spin chains and cyclic triangulene spin chains in relation to their lengths and shapes. The physical mechanism of local excitation within the triangular alkene unit and the weak charge transfer between the units are discussed. The uniformly distributed electrostatic potential allows the system to have a small permanent dipole moment that blocks the electronic transition in the light excitation such that the electronic transition can only be carried out between adjacent carbon atoms. The one-photon absorption (OPA) spectra and two-photon absorption (TPA) spectra are red-shifted with the addition of triangulene units compared to N = 3TSCs (triangulene spin chains, TSCs). Here, TPA is mainly caused by the first step of the transition. The length of the spin chain has a significant adjustment effect on the photon cross-section. TSCs of different lengths and shapes can control chirality by adjusting the distribution of the electric dipole moment and transition magnetic dipole moment. These analyses reveal the photophysical properties of triangulene and provide a theoretical basis for studying the photophysical properties of triangulene and its derivatives.

Hydrogen physisorption on the (BeO)n, B2H4(Be,Ti), and B6Ti3 metal clusters: a computational study of energies and atomic charges.

The equilibrium structures of BeO clusters and Be,Ti-decorated boranes were computed with the ωB97X-D method and the 6-31G + (2d,2p) and aug-cc-pVTZ basis sets to study their intermolecular interactions with hydrogen molecules. Thermochemical and molecular properties such as the harmonic vibrational frequency, dipole and quadrupole moments, and atomic charges are employed to understand the attractive interactions that control the adsorption process. Comparison of molecular properties and atomic charges of the studied compounds before and after H2 molecule adsorption shows that most of the interactions among the BeO clusters and boranes with H2 molecules constitute a combination of dispersion, electrostatic, and weak charge transfer interactions. Calculated values of Hirschfeld atomic charges and ΔEe (in parenthesis) (BeO)4.8H2 (0.028 e and -2.0kcal.mol-1), (BeO)2.12H2 (0.030 e and -2.8kcal.mol-1), B6Ti3.10H2 (0.045 e and -15.4kcal.mol-1), and B6Ti3+.10H2 (0.058 e and -15.3kcal.mol-1) show qualitative correlation between hydrogen atomic charges and electronic energy of hydrogen interaction. The ωB97X-D/6-31 + G(2d,2p) values of Gibbs free energy at 298.15K for (BeO)4.8H2 B2H4Ti.4H2 and B6Ti3.10H2 clusters are equal to -5.0, -4.9, and -5.1kcal.mol-1, respectively, which are within the range of energy parameters of materials that could be employed in hydrogen storage tanks for light vehicles.

Citric acid-modified MIL-88A(Fe) for enhanced photo-Fenton oxidation in water decontamination

Fe-based metal organic framework with high active site exposure, wide light absorption and fast H2O2 activation are pivotal for photo-Fenton degradation of contaminants. However, insufficient active site exposure, weak visible light adsorption and low charge transfer efficiency in iron-oxo clusters usually lead to the slow Fe(II)/Fe(III) cycle. In this study, we develop a novel citric acid (CA)-modified MIL-88A(Fe) strategy to boost photo-Fenton efficiency by accelerating Fe(II)/Fe(III) cycle for emerging contaminants removal. Relationship between CA coordination mode and photo-Fenton performance was studied by using methylene blue (MB) and carbamazepine (CBZ) as model contaminants. It was found that the degradation rate constants of MIL-88A(Fe)-CA-3 were 6.5 and 2.6 times higher than those in the pristine MIL-88A(Fe) for MB and CBZ degradation, respectively. The optimized MIL-88A(Fe)-CA-3 also exhibited good recyclability, enabling multiple cycles in photo-Fenton reaction. The results of experimental characterizations and density functional theory calculations demonstrated that ligand substitution was conductive to active site exposure, visible light absorption, charge carrier transfer and Fe2+/Fe3+ redox cycle, which are responsible for an improved photo-Fenton performance.

Fluorene pendant-functionalization of poly(N-vinylcarbazole) as deep-blue fluorescent and host materials for polymer light-emitting diodes

π-Electron coupling of pendant conjugated segment in π-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons, which is harmful to the performance and stability of deep-blue polymer light-emitting diodes (PLEDs). Herein, considerate of “defect” carbazole (Cz) electromers in poly(N-vinylcarbazole) (PVK), a series of fluorene units are introduced into pendant segments (PVCz-DMeF, PVCz-FMeNPh and PVCz-DFMeNPh) to suppress the strong π-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs. Compared to PVCz-FMeNPh and PVCz-DFMeNPh, PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission, completely similar to its single pendant chromophore, confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments. Therefore, PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity (0.17, 0.08), associated with extremely weak defect emission at 600∼700 nm (induced by carbazole electromers). Finally, PLEDs based on PVCz-DMeF/F8BT blended films (1:1) also present the high maximum luminance (Lmax) of 6261 cd/m2 and current efficiency (CEmax) of 2.03 cd/A, confirmed slightly trapped sites formation. Therefore, precisely control the arrangement and packing model of pendant units in π-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.

Plasmonic features of a hybrid system comprising borophene and aluminium

Due to their intriguing light–matter interactions at the nanoscale, hybrid systems made up of dissimilar elements are currently receiving a lot of attention. In this study, we systematically examine the optical and plasmonic properties of a hybrid system made of borophene and Aluminium (Al) film using first-principles time-dependent density functional theory calculations. We discovered that, despite the weak charge transfer between the constituent systems, the borophene plasmon is totally quenched or damped by the proximity to the Al film for a gap distance (d) below 9 Å, and the Al plasmon dominates the optical response. When the d value is raised to 9 Å and higher, the borophene plasmon starts to reemerge. This finding is consistent with earlier finding on graphene on metallic film, which demonstrated that the graphene plasmons are quenched by the metallic film’s proximity and recovered at high d values.

Moiré-driven reconstitution on electromagnetic energy transfer

The past decade has witnessed an explosion in the field of twistronics concepts, opening the door to numerous extraordinary physical phenomena such as weak ferroelectric charge transfer, superconductivity, topologically protected states, and so on. Here, inspired by the twistronics concepts, we take a moiré three-body system consisting of three metasurfaces supporting highly confined hyperbolic surface plasmons as an example, introducing an analogous concept into the study of near-field electromagnetic energy transfer within three-body system. We demonstrate the possible existence of the moiré transistor effect induced by the twisted hyperbolic repeater in the polariton coupling system (source and drain parallel to each other), where the near-field electromagnetic energy transfer exchanged between the source and the drain can be reversibly switched, amplified, and modulated by action on moiré patterns. Moreover, we point out that for the symmetry-breaking situations (source and drain not parallel to each other), there is also a magic angle in this system and demonstrate that the twisted hyperbolic repeater can act as a moiré compensation effect at this magic angle, mitigating to a certain extent the electromagnetic energy attenuation caused by the malposition between source and drain. Our findings may open new opportunities for the development of near-field thermal energy transport, enabling new perspectives concerning thermal management at the nanoscale, near-field energy conversion, and infrared spectroscopy.

Understanding the Space-Charge Layer in SnO2 for Enhanced Electron Extraction in Hybrid Perovskite Solar Cells.

Tin oxide (SnO2) has been widely used as an n-type metal oxide electron transport layer in perovskite solar cells (PSCs) owing to its superior electrical and optical properties and low-temperature synthesis process. In particular, the interfacial effect between indium tin oxide (ITO) and SnO2 is an important parameter that controls the charge transport properties and device performance of the PSCs. Therefore, understanding the interfacial effect of ITO/SnO2 and its role in PSCs is crucial, but it is not studied intensively. Herein, we investigated the space-charge effect at the interface of ITO/SnO2 using transfer length measurement and conductive atomic force microscopy as a function of SnO2 thickness. Moreover, optical, morphologic, and device measurements were performed to determine the optimal SnO2 thickness for PSCs. The space-charge effect was identified in ITO/SnO2 when the SnO2 layer was very thin due to electron depletion near the interface. Interestingly, a critical kink point was observed at approximately 10 nm SnO2 thickness, indicating the electron depletion and weak charge transfer behavior of the device. Thus, a thickness around 20 nm was favorable for the best PSC performance because charge transport behavior in the thin SnO2 layer was depressed by electron depletion. However, when the thickness of SnO2 exceeded 50 nm, the device performance deteriorated due to increased series resistance. This study provides a strategy to tune the electron transport layer and boost the charge transport behavior in PSCs, making important contributions to optimizing SnO2-based PSCs.

Investigation of the Geometric and Spectroscopic Properties of Four Twisted Triphenylpyridinium Donor-Acceptor Dyes.

The geometric and spectroscopic properties of four cationic N-aryl-2,4,6-triphenylpyridinium-based donor-acceptor dyes─1-[4-(9H-carbazol-9-yl)phenyl]-2,4,6-triphenylpyridinium, 1-[4-(N,N-diphenylamino)phenyl]-2,4,6-triphenylpyridinium, 1-(9-phenyl-9H-carbazol-3-yl)-2,4,6-triphenylpyridinium, and 1-(9-ethyl-9H-carbazol-3-yl)-2,4,6-triphenylpyridinium─are reported. The four dyes exhibited a twisted, quasi-perpendicular geometry about the central donor-acceptor bond, shown by X-ray crystallography and supported by Raman spectroscopy and DFT calculations. The electronic absorption spectra show weak charge transfer (CT) transitions at about 400 nm (ε ∼ 3000 L mol-1 cm-1). Time dependent (TD) DFT supported the nature of the CT transition, displaying an 89-97% shift in electron density from the donor to the acceptor upon electronic excitation. Excited state geometry calculations revealed significant geometry changes upon electronic excitation. Enhancement of vibrational modes attributable to this transition was also recognized in the resonance Raman spectra. Emission spectroscopies showed two distinct emission bands. The lower energy band, resulting from radiative decay of the CT excited state, exhibited large anomalous Stokes shifts of ∼9000 cm-1. Much of the Stokes shift was a consequence of geometry changes between the ground and excited states. This was confirmed by variable temperature emission studies, with Stokes shifts reducing by up to 3000 cm-1 upon cooling from 293 to 80 K. Additionally, a high energy aggregation induced emission band was present for two of the dyes, resulting from the inhibition of excited state geometry reorganization and supported by solid-state emission spectra. These phenomena exemplify the importance of geometry in short range donor-acceptor dyes such as these.

Red Light-Emitting Thermally-Activated Delayed Fluorescence of Naphthalimide-Phenoxazine Electron Donor-Acceptor Dyad: Time-Resolved Optical and Magnetic Spectroscopic Studies.

We prepared an orthogonal compact electron-donor (phenoxazine, PXZ)-acceptor (naphthalimide, NI) dyad (NI-PXZ), to study the photophysics of the thermally-activated delayed fluorescence (TADF), which has a luminescence lifetime of 16.4 ns (99.2 %)/17.0 μs (0.80 %). A weak charge transfer (CT) absorption band was observed for the dyad, indicating non-negligible electronic coupling between the donor and acceptor at the ground state. Femtosecond transient absorption spectroscopy shows a fast charge separation (CS) (ca. 2.02∼2.72 ps), the majority of the singlet CS state is short-lived, especially in polar solvents (τCR = 10.3 ps in acetonitrile, vs. 1.83 ns in toluene, 7.81 ns in n-hexane). Nanosecond transient absorption spectroscopy detects a long-lived transient species in n-hexane, which is with a mixed triplet local excited state (3 LE) and charge separated state (3 CS), the lifetime is 15.4 μs. In polar solvents, such as tetrahydrofuran and acetonitrile, a neat 3 CS state was observed, whose lifetimes are 226 ns and 142 ns, respectively. Time-resolved electron paramagnetic resonance (TREPR) spectra indicate the existence of strongly spin exchanged 3 LE/3 CT states, with the effective zero field splitting (ZFS) |D| and |E| parameters of 1484 MHz and 109 MHz, respectively, much smaller than that of the native 3 NI state (2475 and 135 MHz). It is rare but solid experimental evidence that a closely-lying 3 LE state is crucial for occurrence of TADF and this 3 LE state is an essential intermediate state to facilitate reverse intersystem crossing in TADF systems.

Microscopic Study of Molecular Double Doping

Double doping, in which a single dopant molecule induces two charge carriers in an organic semiconductor (OSC), was recently experimentally observed and promises to enhance the efficiency of molecular doping. Here we present a theoretical investigation of p-type molecular double doping in a CN6-CP:bithiophene-thienothiophene OSC system. Our analysis is based on density functional theory (DFT) calculations for the electronic ground state. In a molecular complex with two OSC oligomers and one CN6-CP dopant molecule, we explicitly demonstrate double integer charge transfer and find the formation of two individual polarons on the OSC molecules and a dianion dopant molecule. We show that the vibrational modes and related infrared absorption spectrum of this complex can be traced back to those of the charged dopant and OSC molecules in their isolated forms. The near-infrared optical absorption spectrum calculated by time-dependent DFT shows features of both typical intramolecular polaron excitations and weak intermolecular charge transfer excitations associated with the doping-induced polaron states.

Chalcogen Bonding in the Molecular Dimers of WCh2 (Ch = S, Se, Te): On the Basic Understanding of the Local Interfacial and Interlayer Bonding Environment in 2D Layered Tungsten Dichalcogenides.

Layered two-dimensional transition metal dichalcogenides and their heterostructures are of current interest, owing to the diversity of their applications in many areas of materials nanoscience and technologies. With this in mind, we have examined the three molecular dimers of the tungsten dichalcogenide series, (WCh2)2 (Ch = S, Se, Te), using density functional theory to provide insight into which interactions, and their specific characteristics, are responsible for the interfacial/interlayer region in the room temperature 2H phase of WCh2 crystals. Our calculations at various levels of theory suggested that the Te···Te chalcogen bonding in (WTe2)2 is weak, whereas the Se···Se and S···S bonding interactions in (WSe2)2 and (WS2)2, respectively, are of the van der Waals type. The presence and character of Ch···Ch chalcogen bonding interactions in the dimers of (WCh2)2 are examined with a number of theoretical approaches and discussed, including charge-density-based approaches, such as the quantum theory of atoms in molecules, interaction region indicator, independent gradient model, and reduced density gradient non-covalent index approaches. The charge-density-based topological features are shown to be concordant with the results that originate from the extrema of potential on the electrostatic surfaces of WCh2 monomers. A natural bond orbital analysis has enabled us to suggest a number of weak hyperconjugative charge transfer interactions between the interacting monomers that are responsible for the geometry of the (WCh2)2 dimers at equilibrium. In addition to other features, we demonstrate that there is no so-called van der Waals gap between the monolayers in two-dimensional layered transition metal tungsten dichalcogenides, which are gapless, and that the (WCh2)2 dimers may be prototypes for a basic understanding of the physical chemistry of the chemical bonding environments associated with the local interfacial/interlayer regions in layered 2H-WCh2 nanoscale systems.

Rational molecular design of phenanthroimidazole-based fluorescent materials towards high-efficiency non-doped deep blue OLEDs

The non-doped device of novel deep-blue emission material PPI-3-SBF with weak intramolecular charge transfer characteristics achieves a maximum EQE of 8.41% with CIEy= 0.07.

Growth direction dependent separate-channel charge transport in the organic weak charge-transfer co-crystal of anthracene-DTTCNQ.

Co-crystallization is an efficient way of molecular crystal engineering to tune the electronic properties of organic semiconductors. In this work, we synthesized anthracene-4,8-bis(dicyanomethylene)4,8-dihydrobenzo[1,2-b:4,5-b']-dithiophene (DTTCNQ) single crystals as a template to study the crystal growth direction dependent charge transport properties and attempted to elucidate the mechanism by proposing a separate-channel charge transport model. Single-crystal anthracene-DTTCNQ field-effect transistors showed that ambipolar transport properties could be observed in all crystal growth directions. Furthermore, upon changing the measured crystal directions, the electronic properties experienced a weak change from n-type dominated ambipolar, balanced ambipolar, to p-type dominated ambipolar properties. The theoretical calculations at density functional theory (DFT) and higher theory levels suggested that the anthracene-DTTCNQ co-crystal motif was a weak charge-transfer complex, in line with the experiment. Furthermore, the detailed theoretical analysis also indicated that electron or hole transport properties originated from separated channels formed by DTTCNQ or anthracene molecules. We thus proposed a novel separate-channel transport mechanism to support additional theoretical analysis and calculations. The joint experimental and theoretical efforts in this work suggest that the engineering of co-crystallization of weak charge-transfer complexes can be a practical approach for achieving tuneable ambipolar charge transport properties by the rational choice of co-crystal formers.

Peri-N-amine-perylenes, with and without phenyl bridge: Photophysical studies and their OLED applications

Donor-bridge-acceptor framework has been studied widely for their detailed photophysical properties with the aim of efficient long range charge transfer. Carbazole attached with electron acceptors has been used for charge transfer properties, thermally activated delayed fluorescence, exciton dynamics etc. In this study, we synthesized donor–acceptor dyads of seconday amine (carbazole and diphenyl amine) attached to perylene through nitrogen, with phenyl (P-Ph-N-CBZ and P-Ph-N-BP) and without phenyl (P-N-CBZ and P-N-BP). Further their detailed photophysical and electroluminescent properties are discussed. P-N-BP is known and is used as standard in this work. DFT studies show nearly orthogonal geometry of P-N-CBZ with the dihedral angle of ∼ 71° between the planes of perylene and carbazole. For P-Ph-N-BP and P-Ph-N-CBZ, the perylene and amines are adopting almost co-planar geometries. Emission spectra of P-Ph-N-CBZ and P-N-CBZ in dichloromethane are structural with clear vibronic features while for P-Ph-N-BP and P-N-BP, the emission is structureless and broad indicating prominent electronic coupling between molecular orbitals of donor and acceptor in the latter case. Fluorescence quantum yields of phenyl-linked dyads are found to be higher than directly linked perylene-amine derivatives. High quantum yield (0.79) in non-polar hexane and polar DMSO (0.66) is observed for P-Ph-N-CBZ. It is interesting to note that the fluorescence lifetimes of these dyads are increasing while fluorescence quantum yields are decreasing with increasing polar solvents, suggesting that the emission has a significant contribution from the 1CT state. Dipole moments estimated from DFT studies and photophysical methods are higher for phenyl-linked dyads than those directly attached which is also consistent with their solvatochromism properties. Weaker electronic coupling in phenyl-linked dyads resulted due to the long distance between donor and acceptor in phenyl-linked dyads. Furthermore application in OLEDs was shown for P-Ph-N-CBZ and P-Ph-N-BP. OLEDs of P-Ph-N-BP showed a peak emission at 568 nm resulting in an amber device. A high luminance of 4.3 × 103 Cd/m2 at a current density of 100 mA/cm2 and a maximum EQE of 4.2% with a low turn on volatage of ∼ 4 V was obtained for these devices. Thus, our results show that weaker charge transfer takes place in perylene based donor–acceptor dyads resulting in bright OLED devices.

Chlorination Enabling a Low-Cost Benzodithiophene-Based Wide-Bandgap Donor Polymer with an Efficiency of over 17.

Three regioregular benzodithiophene-based donor-donor (D-D)-type polymers (PBDTT, PBDTT1Cl, and PBDTT2Cl) are designed, synthesized, and used as donor materials in organic solar cells (OSCs). Because of the weak intramolecular charge-transfer effect, these polymers exhibit large optical bandgaps (>2.0eV). Among these three polymers, PBDTT1Cl exhibits more ordered and closer molecular stacking, and its devices demonstrate higher and more balanced charge mobilities and a longer charge-separated state lifetime. As a result of these comprehensive benefits, PBDTT1Cl-based OSCs give a very impressive power conversion efficiency (PCE) of 17.10% with a low nonradiative energy loss (0.19eV). Moreover, PBDTT1Cl also possesses a low figure-of-merit value and good universality to match with different acceptors. This work provides a simply and efficient strategy to design low-cost high-performance polymer donor materials.

Charge Transfer, Intersystem Crossing, and Electron Spin Dynamics in a Compact Perylenemonoimide-Phenoxazine Electron Donor-Acceptor Dyad.

With phenoxazine (PXZ) as the electron donor and perylene-3,4-dicarboximide (PMI) as the electron acceptor, we prepared a compact, orthogonal electron donor-acceptor dyad (PMI-PXZ) to study the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC). A weak charge transfer (CT) absorption band, due to S0 → 1CT transition, was observed (ε = 2840 M-1 cm-1 at 554 nm, FWHM: 2850 cm-1), which is different from that of the previously reported analogue dyad with phenothiazine as the electron donor (PMI-PTZ), for which no CT absorption band was observed. A long-lived triplet state was observed (lifetime τT = 182 μs) with nanosecond transient absorption spectroscopy, and the singlet oxygen quantum yield (ΦΔ = 76%) is higher than that of the previously reported analogue dyad PMI-PTZ (ΦΔ = 57%). Ultrafast charge separation (ca. 0.14 ps) and slow charge recombination (1.4 ns) were observed with femtosecond transient absorption spectroscopy. With time-resolved electron paramagnetic resonance spectroscopy (TREPR), we confirmed the SOCT-ISC mechanism, and the electron spin polarization phase pattern of the triplet-state TREPR spectrum is (e, e, a, e, a, a), which is dramatically different from that of PMI-PTZ (a, e, a, e, a, e), indicating that the triplet-state TREPR spectrum of a specific chromophore in the electron donor-acceptor dyads is not only dependent on the geometry of the dyads but also dependent on the structure of the electron donor (or acceptor). Even one-atom variation in the donor structure may cause significant influence on the electron spin selectivity of the ISC of the electron donor-acceptor dyads.

Spiro−type TADF emitters based on acridine donors and anthracenone acceptor

Two rigid spiro-type TADF emitters (CBZANQ, PXZANQ) were designed and synthesized via a two-step route. CBZANQ and PXZANQ both contain an anthracenone acceptor along with a carbazole‒acridine-fused donor and a phenoxazine‒acridine-fused donor, respectively, where each donor and acceptor are linked by a spiro bridge to form D-σ-A structures with an orthogonal arrangement. Both CBZANQ and PXZANQ have the difference between the singlet and triplet energy values (ΔEST) of 0.05 eV and 0.03 eV, respectively, which are sufficiently small for efficient triplet harvesting. CBZANQ with a weak electron donor (carbazole) exhibited a weak intramolecular charge transfer (ICT) character, resulting in a low photoluminescence quantum yield (PLQY) of 18%. On the other hand, when combined with a strong electron donor (phenoxazine), PXZANQ exhibited a strong ICT character, resulting in a high PLQY of 71%. Organic light-emitting diode (OLED) devices based on CBZANQ emitter and bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO) host exhibited sky-blue electroluminescence (EL) at 492 nm with a low external quantum efficiency (EQE) of 6.7%. Conversely, the OLED devices fabricated using PXZANQ emitter and DPEPO host exhibited green emission at 528 nm, along with a high EQE of 22.1%. Additionally, the efficiency of PXZANQ-based devices remained high at high luminance, indicating relatively small efficiency roll-off (13.9% EQE under 500 cd/m2).

Multifaceted moiré superlattice physics in twisted WSe2 bilayers

Lattice reconstruction in twisted transition-metal dichalcogenide (TMD) bilayers gives rise to piezo- and ferroelectric moir\'e potentials for electrons and holes, as well as a modulation of the hybridisation across the bilayer. Here, we develop hybrid $\mathbf{k}\cdot \mathbf{p}$ tight-binding models to describe electrons and holes in the relevant valleys of twisted TMD homobilayers with parallel (P) and anti-parallel (AP) orientations of the monolayer unit cells. We apply these models to describe moir\'e superlattice effects in twisted WSe${}_2$ bilayers, in conjunction with microscopic \emph{ab initio} calculations, and considering the influence of encapsulation, pressure and an electric displacement field. Our analysis takes into account mesoscale lattice relaxation, interlayer hybridisation, piezopotentials, and a weak ferroelectric charge transfer between the layers, and describes a multitude of possibilities offered by this system, depending on the choices of P or AP orientation, twist angle magnitude, and electron/hole valley.

Radical-Doped Crystalline Lanthanide-Based Photochromic Complexes: Self-Assembly Driven by Multiple Interactions and Photoswitchable Luminescence.

Stimuli-responsive functional materials, especially the light stimulation color change and tunable fluorescent materials, have received considerable attention because of their broad applications in smart materials. Herein, a series of lanthanide-based [Ln = Nd(III) (1), Sm(III) (2), Eu(III) (3), Gd(III) (4), Tb(III) (5), Yb(III) (6), and Lu(III) (7)] crystalline complexes were attained by simply adding the aqueous lanthanide nitrate solution to the water-soluble naphthalenediimide derivative. The obtained lanthanide-based crystalline materials not only show significant photochromism but also possess reactive organic radicals under ambient conditions. Intriguingly, photoswitchable near-infrared (NIR) fluorescence was realized in the crystalline complex 1. The structures of these crystalline materials were systematically studied to clarify the weak interaction-assisted charge-transfer process. The underlying multiple-interaction-assisted supramolecular self-assembly, the radical-doped nature, and the corresponding photochromic mechanism were thoroughly unearthed by single-crystal X-ray diffraction, in situ solid-state UV-vis diffuse reflectance, and electron paramagnetic resonance spectrometric analysis.