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Harnessing Biofilm Scaffold for Structurally Adaptative Slippery Surfaces with Integrated Antifouling and Anticorrosion Properties
AbstractArtificial liquid‐repellent surfaces are highly desirable to combat pervasive biofouling and corrosion in biological environments. However, existing strategies often suffer from slow binding kinetics and harsh fabrication conditions, hindering the concurrent integration of liquid repellency, universal adhesion, and robust flexibility. Herein, we report that it is possible to engineer microbial biofilms as eco‐friendly, cohesive, and flexible materials for omniphobic slippery coatings fulfilling all these requirements. Unlike conventional synthetic slippery coatings requiring laborious surface pretreatments, biofilm sheets formed on demand assemble a durable nanotextured framework on diverse substrates with multiple material categories and surface topologies, serving as hydrophobic lubricant reservoirs. Employing this renewable material enables the scalable and sustainable coating production. The resulting optically transparent and highly flexible coatings manifest exceptional self‐cleaning properties, readily shedding both waterborne and oily liquids over a broad viscosity range. Notably, the synergy between the corrosion‐protective extracellular matrix and nonstick slipping motion confers unprecedented antibiofouling efficacy and corrosion resistance. This study offers a distinctive perspective on harnessing ubiquitous native biofilms as biomaterials for self‐adaptive coatings, facilitating tailored functionality across broad applications.
Stimuli‐Responsive Equilibrium in N‐Heterocyclic Carbene‐Supported Transition Metal Complexes: Selective Isolation of Multinuclear Species
AbstractThe AgI–N‐heterocyclic carbene (NHC) complexes (3a,b) derived from bis(NHC) ligand 1, which exhibit a temperature‐ and concentration‐dependent equilibrium between the trinuclear and tetranuclear forms, has been successfully isolated, which is slow on NMR time scale. Intriguingly, by freezing this slow equilibrium, facilitated by strong and stable H‐bonding, we could achieve selective isolation of the tetranuclear species (3a,b‐II). On the other hand, encapsulation of an anionic guest, ClO4, led to exclusive formation of the guest encapsulated trinuclear AgI‐NHC complex, 3a‐I. This is unprecedented and marks the first instance where selective isolation of both the species involved in an equilibrium using a C‐donor ligand could be attained. In contrast, distinct behavior was observed with the AuI ion, possessing the same linear geometry, however, with stronger M–CNHC bonds. In this context, a stable non‐exchangeable ≈1:1 mixture (4a,b) of the tri‐ and tetranuclear AuI‐NHC complexes were obtained via transmetalation of both equilibrating (3a,b) and the H‐bonded tetranuclear AgI‐NHC complexes (3a,b‐II). Moreover, by aptly adjusting the reaction parameters of transmetalation process, the trinuclear AuI‐NHC complex (4a,b‐I) could indeed be obtained selectively. Overall, this study highlights a pioneering approach for the control of an equilibrium between different nuclearity metallo‐supramolecular species engaging C‐donor ligands.
Exceptionally High Two‐Photon Absorption Cross Sections in Quinoidal Diazaacene‐Bithiophene Derivatives
AbstractThis study addresses the two‐photon absorption (2PA) properties of (azaacene‐annulated) heterophenoquinones through a synergistic approach combining detailed experimental and theoretical analyses. Exceptionally large 2PA cross sections are found over a broad spectral range in the near‐infrared spectral region, with values up to 4100 GM in the 1400–1600 nm range and even higher values of up to 51770 GM in the 850–950 nm range, which is outstanding for organic chromophores of this molecular size. Our quantum chemical calculations support the experimental findings and elucidate the underlying absorption mechanism leading to the corresponding 2PA properties. The occurrence of such large cross sections is explained by the high oscillator strength of the first excited singlet state and its strong coupling to higher excited electronic states. The large (state‐to‐state) transition dipole moments originate from the acceptor–π–donor–π–acceptor structure of the parent quinoidal bithiophene motif common to all compounds, which in addition also enables their optimal (anti)parallel alignment due to its symmetry and linearity.
Interfacial Mesochannels as Cation Pump for Enhanced Osmotic Energy Harvesting
AbstractMembranes integrating 1D materials are rapidly emerging as highly promising platforms for osmotic energy harvesting. However, their power output is often constrained by insufficient ion selectivity. Herein, we demonstrate a cation pumping strategy by designing mesoporous silica coated multiwalled carbon nanotubes/aramid nanofiber (MCNTs@mSiO2/ANF) composite membranes as osmotic power generators. Cations can be initially enriched in the negatively charged and small‐pore‐sized (∼ 3 nm) interfacial mesopore channels, establishing a strong cation concentration gradient toward the interfiber nanochannels. The gradient continuously drives cations into the interfiber pores, facilitating charge separation, and improving ion selectivity. Additionally, the hydrophilic nature of the mesoporous silica shells promotes ion transport and contributes to high ion flux. Consequently, the fabricated MCNTs@mSiO2/ANF composite nanochannel membranes can deliver a notable power density of 8.24 W m−2 with an excellent ion selectivity of 0.91 under a 50‐fold NaCl salinity gradient. Importantly, the membranes demonstrate long‐term stability for osmotic energy capturing. When placed between natural seawater and river water, the composite membranes yield an impressive power density of 9.93 W m−2, surpassing that of the state‐of‐the‐art 1D material‐based membranes. This work paves the way for the practical applications of nanofiber‐based membranes in sustainable osmotic energy conversion.
Chiral Zinc Sulfide Nanoparticles Scavenging Reactive Oxygen Species for Remodeling Intestinal Homeostasis
AbstractElevated levels of reactive oxygen species (ROS) and gut microbiota dysbiosis are crucial factors that exacerbate inflammatory bowel disease (IBD). To address this, we successfully synthesized zinc sulfide nanoparticles (ZnS NPs) with a particle size of approximately 500 nm and a maximum g‐factor of 0.07, utilizing l‐/d‐cysteine as chiral ligands. Chirality gives NPs unique bioactivity. These chiral ZnS NPs could enter macrophages through the CD44 and clathrin pathways, which enhanced the ability to scavenge ROS, in turn significantly inhibited the NF‐κB and NLRP3 signaling pathways, thereby reducing the secretion of TNF‐α, IL‐6, and IL‐1β, while upregulating IL‐10. In vivo experimental data showed that l‐ZnS NPs outperformed 5‐aminosalicylic acid, significantly improving body weight, reducing the IBD activity index, and attenuating tissue damage. Concurrently, l‐ZnS NPs exhibited a marked prophylactic effect. The benchmark studies verified that l‐ZnS NPs increased the abundance of the beneficial Lachnospiraceae NK4A136 by 10.55‐fold and decreased harmful Enterobacter by 2914.00‐fold, thereby reshaping the intestinal microecological balance. Pharmacokinetic and biosafety assessments confirmed the safety of l‐ZnS NPs. Our findings indicate that chiral ZnS NPs hold great potential as nanodrugs for the treatment and prevention of IBD, providing an important foundation for the development of IBD therapeutic strategies.
Aminomethyl Phosphonic Acid as Highly Effective Multifunctional Additive for Modification of Electron Transport Layer and Perovskite in Photovoltaic Solar Cells
AbstractThe passivation of detrimental perovskite‐based defects is critically acknowledged for fabricating highly effective perovskite solar cells (PSCs). The presence of a high‐quality electron transport layer (ETL) is also considered a pivotal factor for effective charge extraction and transport dynamics. Herein, a simple small organic molecule, aminomethyl phosphonic acid (AMPA), is introduced as a multifunctional additive in the SnO2 ETL. The defects in the SnO2 ETL are effectively suppressed by passivating the oxygen vacancies upon the SnO2 surface. Simultaneously, the carrier mobility and crystallinity of SnO2 are enhanced, and the upward‐regulated conduction band minimum (CBM) is beneficial for constructing a favorable energy level alignment with the perovskite layer. Notably, the introduced residuals on the SnO2 surface can function as crystalline seeds for growth of large perovskite grains, which can passivate the defects in the perovskite bulk phase, boundaries, as well as the SnO2/perovskite interface. Consequently, the power conversion efficiency (PCE) value of the AMPA‐modified PSCs is enhanced from 19.91% to 24.22%. Most importantly, the unencapsulated PSCs with AMPA maintained 94.9% of the initial PCE during 720 h of storage at a relative humidity of 10%, attributed to the improved hydrophobicity of both the SnO2 and perovskite layers after AMPA modification.
Antisolvent‐Regulated Anionic Coordination Enabling Stable Li Metal Anode in Urea‐Based Electrolyte
AbstractThe fabrication of NO3− anion‐participating solvation sheaths to derive inorganic‐rich solid electrolyte interphase (SEI) layers is critical for enhancing the stabilization of lithium metal batteries (LMBs). However, the application of LiNO3 salt is limited by its low solubility and the challenge of controlling NO3− coordination, primarily due to its high donor number. Herein, we demonstrate an antisolvent‐enhanced anionic coordination effect in urea‐based LiNO3 electrolytes for boosting the cycling stability of LMBs. We find that the incorporation of 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether (TTE) into these electrolytes enhances the interaction between the NO3− anion and urea‐based solvent to Li+ in the solvation sheath, resulting in an increase in ion‐pair formation. This also induces a transformation of the NO3− anion from a monodentate to a bidentate coordination configuration, facilitating preferential nitrate reduction at the anode interface. The optimized electrolyte formulation demonstrates remarkable cycling stability in lithium metal anode, achieving 6000 h of operation in a Li||Li cell and a high Coulombic efficiency of 99.6% in a Li||Cu cell. In full‐cell testing, Li||LiFePO4 cells (N/P = 3) maintain 88% capacity retention after 100 cycles at 0.2C.
Removing α‐H in Carboxylate‐Based Electrolytes for Stable Lithium Metal Batteries
AbstractAlthough carboxylate esters greatly improve the cold weather performance of graphite‐based lithium‐ion batteries utilized in arctic expeditions, the underlying cause of the incompatibility between carboxylates and lithium (Li) anodes has not been sufficiently explained, resulting in the greatly restricted usage of carboxylate in lithium metal batteries (LMBs). Herein, we reveal the serious parasitic reactions between carboxylate α‐H atoms and Li metal are the culprits that render carboxylate‐based ineffectiveness for LMBs. By replacing all α‐H atoms with fluorine atoms and methyl groups, we successfully construct inert carboxylates and find the ions/molecules distribution in electric‐double‐layer (EDL) can be manipulated at a molecular‐level. The unique structure ensuring more anions are positioned closer to the Li surface in the EDL of the inert carboxylate‐based electrolyte, the morphology of the deposited Li is significantly regulated and the chemical corrosion gets effectively inhibited, as a consequence of remarkable extending lifespan of carboxylate‐based LMBs with routine salt concentration and few additives. More generally, using carboxylates lacking α‐H atoms offer a realistic approach to increase the variety of solvents that can be used in LMBs electrolytes.
Cation‐Anion‐Engineering Modified Oxychloride Zr‐Based Lithium Superionic Conductors for All‐Solid‐State Lithium Batteries
AbstractWithin the family of halide solid electrolytes (SEs), Li2ZrCl6 demonstrates high oxidative stability, cost‐effectiveness, and mechanical deformability, positioning it as a promising candidate for SEs. However, the application of Li2ZrCl6 as a SEs was hindered by its low ionic conductivity at room temperature. Current strategies to enhance the ionic conductivity of Li2ZrCl6 primarily are focused on single cation or anion sublattice‐engineering, each with distinct advantages and limitations. Here, we propose a novel cation and anion‐sublattice‐engineering strategy, termed CASE, to increase the amorphous content and thus enhance ionic conductivity. The incorporation of Cu2+ and O2− induces distinctive structural modifications within Li2ZrCl6. This structure corroborated through analytic data of X‐ray absorption spectroscopy, the neutron diffraction, and ab initio molecular dynamics. Consequently, the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 achieves an enhanced ionic conductivity of 2.05 mS cm−1 at 25 °C. Furthermore, all‐solid‐state lithium batteries utilizing the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 as an electrolyte and LiNi0.83Co0.11Mn0.06O2 as a cathode exhibit a superior long‐term cycling stability retaining 90.3% of capacity after 1000 cycles at 2 C under room temperature, which are much higher than those of Zr‐based halide electrolytes in publications. Such a result might stimulate the development of more amorphous structures with high ionic conductivity in the CASE strategy.
Steric Coordinated Electrolytes for Fast‐Charging and Low‐Temperature Energy‐Dense Lithium‐Ion Batteries
AbstractElectrolytes are known as the dominant factors for fast‐charging affordability and low‐temperature capability of lithium‐ion batteries (LIBs). Unfortunately, the current electrolytes can hardly simultaneously satisfy all the required characteristics, including sufficient ion transport, high oxidation/reduction interfacial stability, and fast de‐solvation process over a wide‐temperature range. Here, we report a solution by designing electrolyte solvents that coordinate with Li+ in steric configuration. The steric coordinated electrolytes (SCEs) can overcome the dilemma of quasi‐planer coordinated ether electrolytes that has to be weakly coordinated with Li+ to avoid solvent co‐intercalation towards graphite (Gr) anode, therefore enabling the merits including sufficiently dissociation of Li‐salt with high ionic conductivity, low de‐solvation energy, and forming electrode‐electrolyte interphase with low energy barrier. As results, the SCEs with only single‐salt and single‐solvent (trimethoxymethane) achieve fast kinetics towards Gr anode and high oxidation stability. The LiNi0.8Co0.1Mn0.1O2 (NCM811)||Gr LIBs can reach 80% state of the charge in 6 min, and the Ah‐level energy‐dense pouch cells (4.5 V) retain 82.96% (500 cycles) and 85.94% (200 cycles) of initial capacities at room temperature and −20 °C, respectively. Our work deepens the fundamental understanding of Li‐ion solvation structures and affords an effective approach to design sustainable fluro‐free electrolytes for battery systems.
Membrane‐Bounded Intracellular E3 Ubiquitin Ligase‐Targeting Chimeras (MembTACs) for Targeted Membrane Protein Degradation
AbstractTargeted protein degradation (TPD) represents a potent therapeutic strategy aimed at dismantling disease‐associated target proteins. PROTAC is the most widely developed technique for intracellular protein degradation, while its degradation ability on membrane proteins has been hindered by the need for complex synthetic processes and limited permeability. In this study, we developed the membrane‐bounded intracellular E3 ubiquitin ligase‐targeting chimeras (MembTACs) that simultaneously recruit intracellular E3 ubiquitin ligase and bind to the desired membrane proteins for targeted degradation of membrane proteins. We demonstrate that the MembTACs can effectively utilize intracellular E3 ubiquitin ligase to degrade the therapeutically relevant membrane proteins of EpCAM and Met via the proteasome pathway. We anticipate that the new platform will expand the range of PROTAC applications and provide a new dimension for targeted membrane protein degradation.
Controlled Catalysis Delivering High Molecular Weight Polyesters as Recyclable Alternatives to Polystyrenes
AbstractAn organometallic Al(III)K(I) catalyst shows exceptional control in the epoxide/anhydride ring opening copolymerization (ROCOP), producing high molecular weight polyesters (Mn ∼ 100 kg·mol−1). The catalysis is highly effective using cyclohexene oxide, cyclopentane oxide, substituted cyclohexene oxide, and butylene oxide, each combined with phthalic anhydride. The polyesters show entanglement molecular weights, determined by oscillatory shear rheology, from 13 to 50 kg·mol−1 with cyclopentene and substituted cyclohexene moieties being particularly effective (highly entangled). The lead polyesters show high glass transition temperatures (94 °C < Tg < 137 °C), high tensile strengths (40 MPa < σ < 47 MPa) and tensile modulii (0.6 GPa < Ey < 0.9 GPa); their properties are similar to polystyrene. The polyesters are all recyclable by repeated cycles of compression molding, and show equivalently high thermal‐mechanical performances even over repeated recycles.
A High‐Efficiency Ultraviolet Organic Light‐Emitting Diode Employing a Double Boron–Oxygen–Nitrogen‐Based Emitter
AbstractDesigning high‐efficiency ultraviolet organic light‐emitting diodes (UV OLEDs) remains challenging due to the need for efficient utilization of triplet excitons while maintaining a wide bandgap. In this study, we designed double boron–oxygen–nitrogen‐based polycyclic aromatic hydrocarbons (dBON‐PAHs) with rigid planar structures and developed a novel UV emitter, BO‐N, featuring hybridized local and charge‐transfer (HLCT) properties. BO‐N exhibited UV emission in toluene solution and 1,3‐di(9H‐carbazol‐9‐yl)benzene (mCP) film, with photoluminescence (PL) peaks of 391 and 400 nm and narrow full width at half‐maximum (FWHM) values of 15 and 34 nm, respectively. The device doped with 5 wt% BO‐N achieved a narrowband UV emission with an FWHM of 37 nm, an electroluminescence peak (λEL) of 399 nm, and CIE coordinates of (0.166, 0.030). Moreover, the device attained a record‐high maximum external quantum efficiency (EQEmax) of 18.6% among reported HLCT‐based UV OLEDs with CIEy < 0.05. These findings highlight the great potential of double BON‐PAHs as robust emitters for high‐performance UV OLEDs.
Dual‐Responsive Phosphorus‐Based Fluorescent Sensors: Synthesis and Selective Metal Sensing of Pyrazolyl Phosphine Oxides
Abstract Despite a wealth of previously reported frameworks for fluorescent metal sensors, there are few examples of phosphorus‐based fluorophores being used in metal sensing applications. Here, we report the synthesis and characterization of a new family of pyrazolyl phosphine oxides and their use in metal sensing applications. The mechanism of their formation has been probed in detail with both computational and experimental studies, rationalizing the selectivity of the reaction. Their use as dual‐responsive fluorescent metal sensors is then demonstrated, with “turn‐off” and “turn‐on” responses observed for Fe 3+ and Al 3+ , respectively. These systems exhibit good selectivity, large Stokes shifts, and submicromolar limits of detection and will open new avenues in phosphorus‐based fluorophores and metal‐sensing applications.
Photo‐Self‐Fenton Reaction Mediated by Silver Single Atom and Cluster Photocatalysts for Highly Selective Generation of Singlet Oxygen Toward Efficient Organic Wastewater Treatment
AbstractThe persistent organic pollutants in wastewater have caused a heavy threat to ecosystems and humans, but selective removal of these pollutants still faces challenges due to low efficiency, extra addition of oxidation agents, and many highly toxic intermediate products. Herein, we report an efficient, fast kinetic conversion via a photo‐self‐Fenton‐like system of *OOH intermediate‐involved oxidation pathway with a high selection generation of singlet oxygen (1O2) from the novel in situ H2O2 heterolytic activation route for the first time. The single‐atom and cluster‐doped zinc oxide (AgSA–AgC/ZnO) was successfully synthesized to achieve the 100% degradation yield and 80% total of carbon (TOC) of the p‐chlorophenol (4‐CP) as the typical pollutant under solar‐light irradiation and exhibit long‐term activity in a self‐designed photo‐Filter reactor for 4‐CP degradation. It was attributed to the accelerated cycles from Aghighδ+ site to Aglowδ+ site in Fenton‐like catalysis, achieving the rapid selection conversion from the H2O2 heterolytic cleavage to ∼100% 1O2 via the intermediate *OOH at the Ag SA sites for ring‐opening reaction and reactive H* at the Ag clusters sites for dechlorination reaction, respectively. This discovery gives the deep understanding of the high‐performance photo‐self‐Fenton reaction through in situ cycles of variable metals for the organic contaminants treatment.
Competitive‐Coordination‐Induced Crystallization Regulation for Efficient and Stable Sn–Pb Perovskite Solar Cells
AbstractThe unbalanced crystallization rate between Sn‐ and Pb‐based perovskites leads to their heterogeneous distribution and inferior quality of Sn–Pb perovskite films. The promising strategy of selective molecular interaction would balance the crystallization rate. However, the deeper selectivity mechanism needs to be considered, particularly in terms of the entire coordination reaction in the perovskite precursor solution. Herein, we take advantage of thermodynamics and molecular orbital theory to reveal the competitive coordination of additive, i.e., methyl 5‐aminolevulinate hydrochloride (5‐AH), with SnI2 and PbI2. The SnI2 competes with PbI2 in coordinating with 5‐AH to form the thermodynamically favored SnI2‐5‐AH adducts with stronger SnI2‐Cl−, thereby mediating the crystallization rate of the Sn‐ and Pb‐based perovskite. Such crystallization regulation improves the composition uniformity and crystallization quality, which effectively suppresses nonradiative recombination. Additionally, the strong interaction between Sn2+ and 5‐AH as well as reductive grain boundaries inhibits the oxidation of Sn2+. Therefore, the optimal devices with 5‐AH exhibit an improved PCE of 23.76% with a high voltage of 0.885 V and long‐term stability.
Sustainable Synthesis of Concentrated Formate via CO<sub>2</sub> Electrolysis Integrated with Cl<sub>2</sub> Formation
AbstractIntegrating CO2 electrolysis with an industrially relevant anodic reaction enhances the economic feasibility and reduces carbon emissions in practical operations. In this study, we present an electrosynthesis strategy that integrates the CO2 reduction reaction to produce concentrated formate solution with the Cl2 formation in cation exchange membrane‐based electrolyzers, scaling from 1 to 100 cm2 electrode areas. Our process, equipped with two automated pH regulation strategies, achieved selectivities over 80% for formate and 95% for chlorine in a 25 cm2 electrolyzer. Additionally, it demonstrated the ability to achieve formate concentrations up to 5.4 M during extended operation periods, establishing a new benchmark for electrochemical formate/formic acid synthesis. Techno‐economic assessment and life cycle assessment further validated the process' sustainability, demonstrating a realistic path to profitability for valuable chemical production from CO2 even without considering potential subsidies and carbon taxes.
Carbon‐Extraction‐Triggered Phase Engineering of Rhodium Nanomaterials for Efficient Electrocatalytic Nitrate Reduction Reaction
AbstractPhase engineering plays a crucial role in tuning the physicochemical properties of noble metal nanomaterials. However, synthesis of high‐purity unconventional‐phase noble metal nanomaterials remains highly challenging via current wet‐chemical methods. Herein, we develop a unique synthetic methodology to prepare freestanding unconventional hexagonal close‐packed (2H) Rh nanoplates (NPLs) via a rationally designed two‐step strategy. By extracting C from pre‐synthesized rhodium carbide of different sizes and morphology, phase‐controlled synthesis of Rh nanomaterials can be achieved. Impressively, the obtained parallelogram 2H Rh NPLs have high phase purity, well‐defined 2H (0001)h and (100)h facets, and good thermostability (stable up to 300 °C). In the proof‐of‐concept electrocatalytic nitrate reduction reaction (NO3RR), the 2H Rh NPLs achieve higher ammonia (NH3) Faradaic efficiency (91.9%) and NH3 yield rate (156.97 mg h−1 mgcat−1) with lower overpotentials compared to the conventional face‐centered cubic (3C) Rh nanocubes with (100)f facets. Density functional theory calculations reveal that the unconventional (0001)h surface has energetically favored NO3RR pathway and stronger H* absorption ability compared to the (100)f surface, which may lead to the higher activity and selectivity of NH3 production on 2H Rh NPLs. This work opens new avenues to the rational synthesis of unconventional‐phase metal nanomaterials and provides important guidelines to design high‐performance electrocatalysts.
Enhancing Heterointerface Coupling for Durable Industrial‐Level Proton Exchange Membrane Water Electrolysis
AbstractThe industrial‐level application of proton exchange membrane water electrolysis (PEMWE) lies in the capacity of operating at high current density in order for higher power density and lower operational cost. However, it poses a significant challenge to the overall performance of catalysts. Heterointerface engineering has emerged as an ideal strategy for addressing the anodic intrinsic activity limitations. Nevertheless, due to the fragile interface structure with weak interactions between different components, it is difficult to maintain the high activity and long‐term stability of heterostructured catalysts. Herein, we report a ternary heterostructured catalyst, RuIrOx–CeO2, featuring a strong‐coupled interface between RuIrOx phase and CeO2 phase. This strong‐coupled interface exhibits both electronic and oxygen interaction, which effectively inhibits the active phase separation. When applied in PEMWE (0.8 mgIr cm−2 for the anode and 0.4 mgPt cm−2 for the cathode), the resultant catalyst expresses impressive activity, achieving a current density of 3.0 A cm−2 at a cell voltage of 1.75 V in PEMWE and demonstrates a stable 2000‐h operation at 5.0 A cm−2 with an imperceptible voltage degradation of <1 µV h−1.
Peripheral Engineering of Multiple‐Resonance Framework Targeting Efficient Organic Lasers
AbstractMultiple‐resonance thermally activated delayed fluorescent (MR‐TADF) emitters have emerged as promising candidates for organic laser applications due to the potential for simultaneously achieving large oscillator strength and triplet utilization. In this study, we investigate the impact of peripheral tert‐butyl (t‐Bu)‐ and phenyl (Ph)‐substituents on the typical 9‐(phenylcarbazol‐3‐yl)‐9H‐carbazole‐3‐carbonitrile (CzBN) MR framework. Although these modifications preserve the frontier molecular orbital distribution with large oscillator strengths, they significantly influence excited‐state dynamics and molecular aggregation even at low doping concentrations. Introducing Ph substituents extends the π–conjugation extension of CzBN, promoting closer molecular packing, detrimental molecular aggregation, and significantly broadening the excited‐state absorption (ESA) band, which negatively impacts lasing performance. In contrast, CzBN‐tBu, incorporating t‐Bu groups as nonconjugated substituents, demonstrated reduced molecular aggregation and a distinct separation between the ESA band and stimulated emission region. Consequently, the optimal distributed feedback lasing performance is achieved by CzBN‐tBu across various doping concentrations, resulting in the lowest lasing threshold of 3.4 µJ cm−2. These findings underscore the impact of inherent aggregation at low doping ratios on lasing activities, highlighting the crucial role of rational peripheral engineering in modulating molecular interactions and excited‐state dynamics, offering design strategies for developing MR lasing molecules.