Manipulation of the Self-Assembly Morphology by Side-Chain Engineering of Quinoxaline-Substituted Organic Photothermal Molecules for Highly Efficient Solar-Thermal Conversion and Applications.

Organic photothermal materials have attracted increasing attention because of their structural diversity, flexibility, and compatibility. However, their energy conversion efficiency is limited owing to the narrow absorption spectrum, strong reflection/transmittance, and insufficient nonradiative decay. In this study, two quinoxaline-based D-A-D-A-D-type molecules with ethyl (BQE) or carboxylate (BQC) substituents were synthesized. Strong intramolecular charge transfer provided both molecules with a broad absorption range of 350-1000 nm. In addition, the high reorganization energy and weak molecular packing of BQE resulted in efficient nonradiative decay. More importantly, the self-assembly of BQE leads to a textured surface and enhances the light-trapping efficiency with significantly reduced light reflection/transmittance. Consequently, BQE achieved an impressive solar-thermal conversion efficiency of 18.16 % under 1.0 kW m-2 irradiation with good photobleaching resistance. Based on this knowledge, the water evaporation rate of 1.2 kg m-2 h-1 was attained for the BQE-based interfacial evaporation device with an efficiency of 83 % under 1.0 kW m-2 simulated sunlight. Finally, the synergetic integration of solar-steam and thermoelectric co-generation devices based on BQE was realized without significantly sacrificing solar-steam efficiency. This underscores the practical applications of BQE-based technology in effectively harnessing photothermal energy. This study provides new insights into the molecular design for enhancing light-trapping management by molecular self-assembly, paving the way for photothermal-driven applications of organic photothermal materials.

Molecular-Level Insight into Impact of Additives on Film Formation and Molecular Packing in Y6-based Organic Solar Cells.

Additive engineering is widely utilized to optimize film morphology in active layers of organic solar cells (OSCs). However, the role of additive in film formation and adjustment of film morphology remains unclear at the molecular level. Here, taking high-efficiency Y6-based OSC films as an example, this work thus employs all-atom molecular-dynamics simulations to investigate how introduction of additives with different π-conjugation degree thermodynamically and dynamically impacts nanoscale molecular packings. These results demonstrate that the van der Waals (vdW) interactions of the Y6 end groups with the studied additives are strongest. The larger the π-conjugation degree of the additive molecules, the stronger the vdW interactions between additive and Y6 molecules. Due to such vdW interactions, the π-conjugated additive molecules insert into the neighboring Y6 molecules, thus opening more space for relaxation of Y6 molecules to trigger more ordered packing. Increasing the interactions between the Y6 end groups and the additive molecules not only accelerates formation of the Y6 ordered packing, but also induces shorter Y6-intermolecular distances. This work reveals the fundamental molecular-level mechanism behind film formation and adjustment of film morphology via additive engineering, providing an insight into molecular design of additives toward optimizing morphologies of organic semiconductor films.

Effects of a long-short axis skeleton on the excited-state properties of ultraviolet hot exciton molecules: luminescence mechanism and molecular design.

Wise design strategies for efficient ultraviolet (UV) hot exciton molecules are highly desired. In this work, inspired by the long-short axis skeleton strategy, a theoretical study on the substituent effect of the long-axis on the photophysical properties of UV hot exciton molecules is performed. A multiscale simulation is performed to study the photophysical properties of the reported compound 2BuCz-CNCz and theoretically designed promising compounds 2Cz-CNCz, 2TPA-CNCz2TPA-CNCz, 2Na-CNCz and 2An-CNCz, which all possess unique features of UV emission and hot exciton properties. The packing modes of the five molecules in a film are obtained by molecular dynamics (MD) simulations, and then the photophysical properties with the consideration of the SSE (solid-state effect) are studied by using the combined quantum mechanics and molecular mechanics (QM/MM) method. Finally, the exciton evolution process is revealed by the rate equations. The results show that different substituents in the long axis have relatively little effect on the larger twist angle in the short axis. The tert-butyl and triphenylamine groups increase the vibration of the molecule, enhance the non-radiative rate of the molecule and intensify the energy dissipation, but the vibration of tert-butyl can be greatly restrained in the solid state. Furthermore, our designed 2Na-CNCz compound possesses the maximum reverse intersystem crossing rate and radiative decay rate. Therefore, when studying the effect of the long-axis substituents on the properties of hot excitons, 2Na-CNCz could be a profitable candidate molecule. This work should enrich the theoretical calculation methods to investigate the luminescence properties of organic molecules in OLEDs.

Organic Electroluminescent Materials Possessing Intra- and Intermolecular Hydrogen Bond Interactions: A Mini-Review.

Organic light-emitting diodes (OLEDs) have become the predominant technology in display applications because of their superior light weight, flexibility, power conservation, and environmental friendliness, among other reasons. The device's performance is determined by the intrinsic properties of organic emitters. The aggregation structure of emitters, in particular, is crucial for color purity and efficiency. Intra- and intermolecular interactions, such as hydrogen bonds (H-bonds), can reduce structural vibrations and torsions, which affect the stability of emitting layer films and optoelectronic properties of emitting materials. Hence, by regulating the H-bond interaction, the desired properties could be obtained. This mini-review focuses on the influence of intra- and intermolecular H-bond interactions on the optoelectronic properties of high-performance emitters.

Theoretical study on the mechanism of hot excitons combined with aggregation-induced emission in efficient red fluorescent molecules.

Fluorescent emitters with the hot exciton mechanism combined with aggregation induced emission (AIE) character show prospective applications in organic light emitting diodes (OLEDs). However, theoretical studies on amorphous states are limited. In this work, a theoretical study is performed on the photophysical properties of the reported compound 4-(7-(10-ethyl-10H-phenothiazin-3-yl)benzo[c][1,2,5]thiadiazol-4-yl)-N,N-diphenylaniline (PBTPA), which possesses a hot exciton mechanism and AIE. The aggregation states of this molecule in a film are given by molecular dynamics (MD) simulations, and then the photophysical properties are studied by using the QM/MM method with the consideration of the solid-state effect (SSE). The results explain the hot exciton and AIE mechanism of the molecule. First, there is a hot exciton channel between the S1 and T2 state of the PBTPA. Second, the conformational changes of PBTPA between the ground state and the excited state are restricted in the aggregate state. Last, in the low frequency region, the rotation motion is suppressed, and then the reorganization energy and Huang-Rhys (HR) factor in the aggregate state are much smaller. Therefore, the molecules show strong fluorescence efficiency in the aggregated state.

Tailored Polymeric Hole-Transporting Materials Inducing High-Quality Crystallization of Perovskite for Efficient Inverted Photovoltaic Devices.

For achieving high-performance p-i-n perovskite solar cells (PSCs), hole transporting materials (HTMs) are critical to device functionality and represent a major bottleneck to further enhancing device stability and efficiency in the inverted devices. Three dopant-free polymeric HTMs are developed based on different linkage sites of triphenylamine and phenylenevinylene repeating units in their main backbone structures. The backbone curvatures of the polymeric HTMs affect the morphology and hole mobility of the polymers and further change the crystallinity of perovskite films. By using PTA-mPV with moderate molecular curvature, p-i-n PSCs with high efficiency of 19.5% and long-term stability can be achieved. The better performance is attributed to the more effective hole extraction ability, higher charge-carrier mobility, and lower interfacial charge recombination. Furthermore, these three polymeric HTMs are synthesized without any noble metal catalyst, and show great advantages in future application owing to the low-cost.

Donor-Acceptor Molecule Based High-Performance Photothermal Organic Material for Efficient Water Purification and Electricity Generation.

In this contribution, a unique donor-acceptor conjugated organic-small-molecule photothermal material, namely GDPA-QCN, is presented. Bulky dendritic triphenylamine (GDPA) was grafted onto quinoxaline-6,7-dicarbonitrile (QCN) with a phenyl ring as a bridge to form an "umbrella" architecture. Benefited from the particular molecular structure, in solid state, GDPA-QCN molecules adopted a loose packing mode due to the steric effect of "umbrella head" dendritic triphenylamine and flexible molecular structure feature, which allows efficient intramolecular motions and consequently elevates energy dissipation by taking the pathway of thermal deactivation within broad absorption range. The GDPA-QCN solid has high solar-thermal conversion efficiency with an absorption range from 300 to 1100 nm, which can promote superior water purification and electricity generation performance.

High-Efficiency, Non-doped, Pure-Blue Fluorescent Organic Light-Emitting Diodes via Molecular Tuning Regulation of Hot Exciton Excited States.

Tremendous efforts have been made on researching triplet-triplet annihilation (TTA) and thermally activated delayed fluorescence (TADF) materials for realizing high-efficiency blue organic light-emitting diodes (OLEDs) through utilizing triplet exciton conversion to the lowest singlet excited state (S1) from the lowest triplet excited state (T1). However, hot exciton conversion from the upper triplet energy level state (Tn, n > 1) to the lowest singlet excited state (S1) is an increasingly promising method for realizing pure-blue non-doped OLEDs with performances comparable to those of TTA and TADF materials. Herein, two pure-blue fluorescent emitters of donor (D)-π-acceptor (A) type, PIAnCz and PIAnPO, were designed and synthesized. The excited-state characteristics of PIAnCz and PIAnPO, confirmed by theoretical calculations and photophysical experiments, demonstrated these materials' hot exciton properties. Based on PIAnCz and PIAnPO as emission layer materials, the fabricated non-doped devices exhibited pure-blue emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.12) and (0.16, 0.15), maximum luminescences of 10,484 and 15,485 cd m-2, and maximum external quantum efficiencies (EQEs) of 10.9 and 8.3%. Besides, at a luminescence of 1000 cd m-2, the EQEs of PIAnPO-based devices can still be high at 7.7%, and the negligible efficiency roll-off was 6.0%. The device performance of both materials demonstrates their outstanding potential for commercial application.

Highly efficient non-doped blue fluorescent OLEDs with low efficiency roll-off based on hybridized local and charge transfer excited state emitters.

Designing a donor-acceptor (D-A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D-π-A fluorescent molecule (triphenylamine-anthracene-phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L'Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A-1, power efficiency of 12.35 lm W-1, luminescence of ≈29 900 cd cm-2, and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m-2 with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.

Feasible structure-modification strategy for inhibiting aggregation-caused quenching effect and constructing exciton conversion channels in acridone-based emitters.

Acridone (ADO) is an anthracene-based derivative that plays an important role in the construction of organic light-emitting diode emitters. However, ADO suffers from an aggregation-caused quenching (ACQ) effect because of its strong intermolecular stacking and tendency to form excimers. In this work, we appended some electron-donating moieties with different rotors and substitution patterns on ADO to prepare six ADO-based derivatives. In addition, a benzonitrile group was introduced onto the nitrogen atom of the ADO unit to fabricate a high-energy charge-transfer (CT) state that formed a reverse intersystem crossing (RISC) channel. Systematic spectral measurements revealed that the rotors effectively suppressed the ACQ effect. In addition, aggregation-enhanced emission (AEE) was observed for the ADO derivatives modified with triphenylamine (TPA) because of the existence of multiple rotors and propeller-like conformation in TPA block. Theoretical calculations and the performance of electroluminescent devices containing the derivatives confirmed that the exciton conversion channel was constructed at the high-energy level and activated during device operation. Although the performance of these ADO-based derivatives was not ideal in terms of efficiency, the results confirmed the feasibility of this structure modification strategy to simultaneously inhibit the ACQ effect and construct excitons conversion channels.

Hybridization and de-hybridization between the locally-excited (LE) state and the charge-transfer (CT) state: a combined experimental and theoretical study.

Excited state properties play a key role in the photoluminescence (PL) and electroluminescence (EL) performance of organic light-emitting diode (OLED) materials. The solvatochromic effects were observed in a series of triphenylamine (TPA)-phenanthroimidazole (PI) derivatives with the increase of solvent polarity, accompanied by the transformation of an excited state character from the locally-excited (LE) state to the charge-transfer (CT) state in the emission spectra. The excited state properties were systematically investigated in these donor-acceptor systems using time-dependent density functional theory (TD-DFT). The hybridization and de-hybridization processes between LE and CT states were resolved with an increasing number of phenyls along horizontal and vertical directions, respectively. We provide a novel insight into the fine modulation of the excited-state characters and compositions in the donor-acceptor system for the new-generation, low-cost and high-efficiency fluorescent OLED materials.

Highly Efficient Nondoped Green Organic Light-Emitting Diodes with Combination of High Photoluminescence and High Exciton Utilization.

Photoluminescence (PL) efficiency and exciton utilization efficiency are two key parameters to harvest high-efficiency electroluminescence (EL) in organic light-emitting diodes (OLEDs). But it is not easy to simultaneously combine these two characteristics (high PL efficiency and high exciton utilization) into a fluorescent material. In this work, an efficient combination was achieved through two concepts of hybridized local and charge-transfer (CT) state (HLCT) and "hot exciton", in which the former is responsible for high PL efficiency while the latter contributes to high exciton utilization. On the basis of a tiny chemical modification in TPA-BZP, a green-light donor-acceptor molecule, we designed and synthesized CzP-BZP with this efficeient combination of high PL efficiency of η(PL) = 75% in the solid state and maximal exciton utilization efficiency up to 48% (especially, the internal quantum efficiency of η(IQE) = 35% substantially exceed 25% of spin statistics limit) in OLED. The nondoped OLED of CzP-BZP exhibited an excellent performance: a green emission with a CIE coordinate of (0.34, 0.60), a maximum current efficiency of 23.99 cd A(-1), and a maximum external quantum efficiency (EQE, η(EQE)) of 6.95%. This combined HLCT state and "hot exciton" strategy should be a practical way to design next-generation, low-cost, high-efficiency fluorescent OLED materials.

Separation of electrical and optical energy gaps: selectively adjusting the electrical and optical properties for a highly efficient blue emitter.

The design concept of separation of optical and electrical bandgap for wide bandgap materials is further developed in DCzSiPI. The HOMO/LUMO levels can be tuned by incorporation of PI and DCz substituents. The tetraphenylsilane core avoids the intramolecular charge transfer from DCz to PI (DCz = dimer carbazole, PI = phenanthro[9,10-d]imidazole). The allowed transitions are found to be from HOMO-1 to LUMO providing DCzSiPI with sufficient bandgap.

Fluorescence detection of trace TNT by novel cross-linking electropolymerized films both in vapor and aqueous medium.

Electropolymerized (EP) films with high fluorescent efficiency are introduced to the detection of trace 2,4,6-trinitrotoluene (TNT). Three electroactive materials TCPC, OCPC and OCz have been synthesized and their EP films have been demonstrated to be sensitive to TNT. Among them, the TCPC EP films have displayed the highest sensitivity to TNT in both vapor and aqueous medium, even in the natural water. It is proposed that the good performances would be caused by the following two factors: first, the cross-linking network of EP films can generate the cavities which benefit the TNT penetration, and remarkably increase the contact area between the EP films and TNT; second, the frontier orbits distribution leads the fast photo-induced electron transfer (PET) from the TCPC EP films to TNT. Our results prove that these EP films are promising TNT sensing candidates and provide a new method to prepare fluorescent porous films.

Enhanced proportion of radiative excitons in non-doped electro-fluorescence generated from an imidazole derivative with an orthogonal donor-acceptor structure.

A greatly enhanced proportion of radiative excitons in non-doped blue electroluminescence with a maximum exciton utilizing efficiency (EUE) of 85% is harvested in the orthogonal cyano substituted, charge transfer (CT) emitter TPMCN, in comparison to the localized emission (LE)-like emitter TPM with a low EUE of 16%.

Electrochemical route to fabricate film-like conjugated microporous polymers and application for organic electronics.

Film-like conjugated microporous polymers (CMPs) are fabricated by the novel strategy of carbazole-based electropolymerization. The CMP film storing a mass of counterions acting as an anode interlayer provides a significant power-conversion efficiency of 7.56% in polymer solar cells and 20.7 cd A(-1) in polymer light-emitting diodes, demonstrating its universality and potential as an electrode interlayer in organic electronics.

A dual channel optical detector for trace water chemodosimetry and imaging of live cells.

A novel 3-5-dichlorosalicylaldehyde Schiff base chemodosimeter (compound 1) for water is designed and synthesized, and it works based on a water-triggered reaction of a Schiff base. Addition of trace amounts of water into 1 in various organic solvents leads to a fluorescence turn-on response and a simultaneous dual-channel signal modulation (both in the fluorescence and absorption spectra). Especially, 1 is found to be an outstanding fluorescence enhancement water sensor in methanol with an extremely low detection limit of 22 ppm. Consequently this probe can be utilized to detect trace water in commercial methanol. The quantitative detection of a wide range of water content is enhanced in THF and acetonitrile (0-35% v/v for THF and 0-20% v/v for acetonitrile), where the fluorescence peak intensity is nearly proportional to the amount of water added. Moreover, 1 can be used for monitoring pH through a novel ON-OFF-ON type signal modulation both in fluorescence and absorption spectra within a wide pH detection range. Thus, the chemodosimeter can not only be utilized to monitor the intracellular pH fluctuations, but also to accomplish simultaneous in situ staining of the cytosol and acidic organelles in two different channels, respectively.

In situ electrochemical deposition and doping of C60 films applied to high-performance inverted organic photovoltaics.

Novel C(60)-based cross-linked films formed by electrodeposition are produced and used as the electron-collection layer in inverted polymer solar cells (PSCs). The electrodeposited films exhibit a low work function of 4.2 eV and the PSCs perform well, with power conversion efficiencies of up to 6.31%. This new kind of electrodeposited film affords more opportunities to develop modified electrodes with a low work function.