Carbonyl Units Research Articles

Design of Thermally Activated Delayed Fluorescence Materials: Transition from Carbonyl to Amide‐Based Acceptor

AbstractBenzophenone skeletons containing a carbonyl unit (O=C) have been widely used as electron acceptors in the thermally activated delayed fluorescence (TADF) materials. Herein, we present a novel molecular design concept for TADF materials by transitioning from a carbonyl to an amide (O=C−N) skeleton as the acceptor. The amide unit, compared to its carbonyl counterpart, offers a more stable electronic configuration. Leveraging this insight, we have developed a series of high‐performance TADF molecules based on benzoyl carbazole and carbazoline acceptors. These molecules exhibit exceptionally small singlet‐triplet energy gaps and pronounced aggregation‐enhanced emission properties, achieving photoluminescence quantum yields in neat films as high as 99 %. Consequently, these materials serve as efficient emitters in non‐doped organic light‐eimtting diodes (OLEDs), reaching a maximum quantum efficiency (EQEmax) of up to 26.0 %, significantly higher than the 17.0 % obtained with benzophenone acceptor‐based TADF molecules. Additionally, they have been used as TADF hosts in narrowband red fluorescent OLEDs, setting a record‐high EQEmax of 22.4 %.

Design of Thermally Activated Delayed Fluorescence Materials: Transition from Carbonyl to Amide-Based Acceptor.

Benzophenone skeletons containing a carbonyl unit (O=C) have been widely used as electron acceptors in the thermally activated delayed fluorescence (TADF) materials. Herein, we present a novel molecular design concept for TADF materials by transitioning from a carbonyl to an amide (O=C-N) skeleton as the acceptor. The amide unit, compared to its carbonyl counterpart, offers a more stable electronic configuration. Leveraging this insight, we have developed a series of high-performance TADF molecules based on benzoyl carbazole and carbazoline acceptors. These molecules exhibit exceptionally small singlet-triplet energy gaps and pronounced aggregation-enhanced emission properties, achieving photoluminescence quantum yields in neat films as high as 99 %. Consequently, these materials serve as efficient emitters in non-doped organic light-eimtting diodes (OLEDs), reaching a maximum quantum efficiency (EQEmax) of up to 26.0 %, significantly higher than the 17.0 % obtained with benzophenone acceptor-based TADF molecules. Additionally, they have been used as TADF hosts in narrowband red fluorescent OLEDs, setting a record-high EQEmax of 22.4 %.

Structure-Glass Transition Relationships in Non-Isocyanate Polyhydroxyurethanes.

The molecular dynamics, with an emphasis on the calorimetric and dynamic glass transitions, of non-isocyanate polyhydroxyurethanes (PHUs) produced by the equimolar polyaddition of polyether-based dicyclic carbonates (P-CCs) and various short diamines was studied. The diamine component consisted of a short aliphatic diamine (1,4-diaminobutane, DAB) and a more complex 'characteristic' diamine. The study was conducted to investigate (i) the chemical structure of the characteristic amine, (ii) its molar ratio, and (iii) the structure and molar mass of the P-CC. Infrared spectroscopy, differential scanning calorimetry, and broadband dielectric spectroscopy were employed. The P-CC, constituting the bulk of the systems, was the most crucial component for the glass transition. The characteristic amine influenced the glass transition as a result of its bulky structure, but also presumably as a result of the introduction of free volume and the formation of hydrogen bonds. The dynamic glass transition (α relaxation) trace in the Arrhenius plots showed a subtle change at a certain temperature that merits further study in the future. The charge mobility was fully coupled with the molecular mobility, as evidenced by dc conductivity being directly proportional to the characteristic frequency of α relaxation. The fluctuation in carbonyl units (β relaxation) was mildly affected by changes in their immediate environment.

Multiple stimuli-responsive low-molecular-weight organogel with room temperature phosphorescence for dynamic anti-counterfeiting

Pure organic luminogens with stimuli-responsive room temperature phosphorescence (RTP) have drawn much attention due to their promising applications in dynamic anti-counterfeiting. In this work, we designed a simple organic molecule with rigid chemical structure (m-FBCM), and all-atom molecular dynamics simulation indicated that it was a potential organogelator. Moreover, the molecule comprises multiple carbonyl units and aromatic rings, which could promote the intersystem crossing process. Our experiments revealed that m-FBCM could form stable gel in DMSO, promoted by balanced intermolecular π-π interactions. Green afterglow was observed at room temperature in the gel state with lifetime 41.6 ms, ascribed to its RTP. The afterglow became invisible at 45 °C and could recover upon cooling to room temperature. Moreover, the N-acylation reaction between m-FBCM xerogel and vapor of volatile primary amine could occur in a few minutes without additional catalyst, providing an orange afterglow. The thermal-responsive and chemical-reponsive properties impart the RTP gel promising application in dynamic anti-counterfeiting.

Carbonyl Chemistry for Advanced Electrochemical Energy Storage Systems.

On the basis of the sustainable concept, organic compounds and carbon materials both mainly composed of light C element have been regarded as powerful candidates for advanced electrochemical energy storage (EES) systems, due to theie merits of low cost, eco-friendliness, renewability, and structural versatility. It is investigated that the carbonyl functionality as the most common constituent part serves a crucial role, which manifests respective different mechanisms in the various aspects of EES systems. Notably, a systematical review about the concept and progress for carbonyl chemistry is beneficial for ensuring in-depth comprehending of carbonyl functionality. Hence, a comprehensive review about carbonyl chemistry has been summarized based on state-of-the-art developments. Moreover, the working principles and fundamental properties of the carbonyl unit have been discussed, which has been generalized in three aspects, including redox activity, the interaction effect, and compensation characteristic. Meanwhile, the pivotal characterization technologies have also been illustrated for purposefully studying the related structure, redox mechanism, and electrochemical performance to profitably understand the carbonyl chemistry. Finally, the current challenges and promising directions are concluded, aiming to afford significant guidance for the optimal utilization of carbonyl moiety and propel practicality in EES systems.

Layer-Ordered Organooxotin Clusters for Extreme-Ultraviolet Photolithography.

Extreme-ultraviolet (EUV) photolithography, which enables the high-throughput production of well-defined patterns with critical dimensions on the scale of several nanometers, is essential for the fabrication of a highly integrated semiconductor. The full exploitation of EUV lithographic techniques necessitates the development of photoresist (PR) materials with both high EUV sensitivity and a long shelf-life. However, despite notable advances, the available library of EUV PR materials remains limited. Here we report EUV PRs capable of forming preorganized layers consisting of ladder-structured tetranuclear stannoxanes. Single-crystal X-ray structure analyses reveal a close interlayer distance of 8.5 Å through interdigitation of the pseudoaxial butyl chains. The developed EUV PR materials exhibit high solubility in organic solvents commonly used in semiconductor processing, enabling the preparation of PR solutions with superior wettability and uniform film-forming ability on Si wafer substrates. These PR solutions also demonstrate notable resistance to hydrolytic decomposition for as long as 1 month, indicating a long shelf-life. Our PR materials enabled negative-tone patterning processes that involved a solubility decrease upon irradiation. The presence of chromophoric ligands makes our PR materials compatible with conventional UV photolithography, through photochemical reactions involving carbonyl units. In addition, e-beam and EUV lithography could produce fine line patterns of our PRs, with critical dimensions of 20 and 15 nm, respectively. Our research showcases the potential of layer-ordered organooxotin clusters for EUV PR applications.

Regulation on photocatalytic debromination by the reconfiguration of carbonyl groups on the covalent organic frameworks

Covalent organic frameworks (COFs) as promising organic semiconductor photocatalysts have become a research hotspot in the field of photocatalytic organic synthesis. Herein, a series of imine-linked EN-COF-x were synthesized by condensation reaction of amine monomer with triformylbenzene monomer. Then, β-ketoamine-linked KE-COF-y were obtained by the reconstruction of EN-COF-x in alkaline solution. The photocatalytic performance of COFs before and after the isomerization from enols to ketones were investigated. The characterization results and density functional theory calculations clearly demonstrated that the carbonyl groups not only make the conduction band energy level more negative, but also lead to a more inhomogeneous charge distribution in the molecule, which improved the separation efficiency of the photogenerated electrons. In addition, the increase in the number of hydroxyl groups on triformylbenzene monomer contributed to the formation of more carbonyl groups in the COF frameworks, which is beneficial to improving its photocatalytic performance. KE-COF-3 synthesized from 2,4,6-Trihydroxy-1,3,5-benzenetricarbaldehyde has more carbonyl group units and more suitable redox potential, which effectively promoted the debromination reaction with 99% yield under light irradiation. Meanwhile, it can be reused at least five times without loss of catalytic activity. This work provides insights for the rational design of functionalized β-ketoamine COFs for photocatalytic organic transformations.

Self-assembled Quinacridone (QA) based polymers with strong hydrogen bonding for OFETs

For totally disordered organic polymer films, charge mobility is low, while the mobility significantly increases if the polymer exhibits self-assembling properties that can be exploited to generate ordered structures. Introducing a hydrogen-bonding functionality in the materials, resulting in hydrogen-bonded material superstructures, can be a suitable method to fulfil those critical requirements. To the best of our knowledge, the chromophores with hydrogen bonding ability are rarely investigated. Quinacridone (QA) with large π-conjugation system, planar structure as well as the amide and carbonyl groups, is attracted our attention. The hydrogen bonding association (NH…OC) can be formed between the amide groups and the carbonyl units from the QA core. In this work, the QA chromophore is, for the first time, introduced as the electron withdrawing unit in donor-acceptor type polymers for semiconductors. The hydrogen bonded polymers exhibit significantly large red shifted up to 192 nm, which indicates that the hydrogen bonding association in the QA system is powerful. In addition, the hydrogen bonding association led to the polymers not only from a disorder state and inferior crystallinity transferring into a more ordered structures with a block- or fiber-liked-shaped crystalline, but also a strong aggregation. This observation is beneficial for the hole transporting between the neighboring molecules. In addition, the HOMO energy levels have been improved after the hydrogen bonding association formation, which is advantage for the Ohmic contact formation. As a consequent, the hole transport mobility is significantly improved from 0.13 cm2 V−1 s−1–1.02 cm2 V−1 s−1. This work demonstrate that QA is a novel and promising electron-deficient building block with potential strong hydrogen bonding association for the high-performance semiconductor.

Easily accessible linear and hyperbranched polyesters as solid polymer electrolytes

Herein we report synthesis, characterization, thermal properties, ionic conductivity and oxidative stability of novel linear and hyperbranched polyesters. Tri-acrylate ester of commercially available 1,1,1-Tris(hydroxymethyl)propane (M1) was used as the primary building block for the synthesis of linear and hyperbranched polymers. A3 + B2 type polycondensation between M1 and dithiols of two different chain lengths (C3, C6) by 100 % atom efficient thiol-acrylate Michael addition reaction, followed by consumption of the unreacted acrylate esters (in the linear or terminal units) with 1-butane thiol produced two hyperbranched polymer namely HB-P1 and HB-P2. For synthesis of linear analogues, one of the equivalent acrylate esters was reacted first with 1-butane thiol and the resulting di-acrylate monomer was polymerized with the C3 and C6-dithiols, producing linear polymers L-P1 and L-P2. All the polymers showed molecular weight (Mn) in the range of 5000–6000 gmol−1 with low dispersity. TGA analysis revealed sufficient thermal stability of the polymers for the application as solid polymer electrolyte. All the polymers are amorphous, showing only a glass transition in the range of ∼ -45 °C (C3 spacer) to −50 °C (C6 spacer) and no crystallization peak. In presence of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt the Tg increased by ∼ 10 °C. Solid polymer electrolytes were prepared by incorporating LiTFSI at a molar ratio of polymer carbonyl units to lithium of C=O/Li of 10 and ionic conductivity (σ) was evaluated by electrochemical impedance spectroscopy (EIS). Moderate values in the range of 10-7 S cm−1 were obtained at 25 °C with slightly higher values for the linear polymers. The ionic conductivity increased up to ∼ 2 orders of magnitude at higher temperatures. The oxidative stability of the polymer electrolytes against lithium-metal electrodes revealed onset potential for the first degradation in the range of 3.8 V, indicating moderate stability that might be suitable for testing applications in all-solid-state lithium-metal batteries using sulfur or lithium iron phosphate cathodes.

Mechanofluorochromic property of coumarin derivatives containing carbonyl group

Four novel coumarin derivatives with different substituents (CMCO-H, CMCO-F, CMCO-CH3 and CMCO-CF3) functionalized by carbonyl unit were designed and synthesized. The relationship between spatial structure and photophysical properties of these coumarin compounds in different states had been systematically studied. In the single molecule state, with the increase of solvent polarities, the fluorescent peaks exhibited obvious solvatochromic effect, accompanied by a decrease in intensity. The significant solvatochromism effect suggested that these four coumarin derivatives both are typical intramolecular charge transfer molecules. The density functional theory calculation results showed that the electron clouds were transferred from coumarin unit and the connected aromatic ring to carbonyl and styrenyl groups. Meanwhile, compounds CMCO-CH3 and CMCO-CF3 exhibited reversible mechanofluorochromic (MFC) property between yellow and orange emission. The single crystal XRD, powder XRD and SEM experiment suggested that the modulation of photophysical properties come from the change of compounds spatial structures. The study provided an efficient way for the design of organic compounds with MFC property.

Helenine blocks NLRP3 activation by disrupting the NEK7-NLRP3 interaction and ameliorates inflammatory diseases.

The involvement of NLRP3 inflammasome is associated with the progress of numerous inflammatory conditions. However, there is currently no single compound used in the clinic. Search for the inhibitor of NLRP3 inflammasome from natural products is an attractive direction. The compound Helenin (Hel), which is obtained from Inula helenium L., is reported to have anti-inflammatory activities. However, the underlying molecular mechanisms and specific inflammatory signal pathway remains not well understood. This research aims to determine the impacts of Hel on NLRP3 inflammasome and the underlying mechanism involved, meanwhile also assessing its potential as a therapeutic intervention for inflammatory diseases mediated by NLRP3 overactivation. Pretreated with Hel in BMDMs (bone marrow-derived macrophages), then stimulated with NLRP3 triggers and measured the expression of active caspase-1 and interleukin 1β (IL-1β). Determination of intracellular K+ and Ca2+, ASC oligomerization and mitochondrial reactive oxygen species (mtROS) production were employed to explore the preliminary mechanism of Hel on NLRP3 activation. Subsequently, Co-immunoprecipitation was used to investigate protein-protein interaction and reduction of covalent bonds of Hel was to explore the binding mode between drugs and proteins. Finally, in vivo experiments, we utilized mouse lethal sepsis and monosodium urate(MSU)-induced peritonitis models to evaluate the effectiveness of Hel in inhibiting inflammatory diseases. The findings revealed that Hel exhibited a specific blocking effect on NLRP3, with no impact on the assembly of NLRC4 and AIM2 inflammasome. Through the analysis of mechanisms targeting key upstream factors in NLRP3 activation, Hel inhibited NLRP3-dependent ASC oligomerization but did not regulating inflammasome priming, K+ efflux, Ca2+ influx, or mitochondrial damage and mtROS. Moreover, Hel effectively interrupted the binding of NEK7-NLRP3, which was dependent on the active double C=C of the α,β-unsaturated carbonyl units in Hel. In mouse models, Hel showed promising therapeutic effects in the treatment of NLRP3 overactivation-associated diseases, including the lethal sepsis and acute systemic inflammation induced by lipopolysaccharide (LPS) and peritonitis induced by MSU. Our results indicate that Hel dependent α,β-unsaturated carbonyl units interrupt the formation of the NLRP3-NEK7 interaction, thereby blocks the inflammasome assemblage and activation. These fundings would suggest that Hel is a promising inhibitor for treating diseases driven by NLRP3 overactivation.

Palladium-catalyzed four-component domino sulfonylation and carbonylation of 1,3-enynes at room temperature

A novel palladium-catalyzed four-component domino sulfonylation and carbonylation of 1,3-enynes has been developed, which enables the rapid incorporation of allene, sulfone, carbonyl and amine units into one single molecule simultaneously.

Discerning toxic nerve gas agents via a distinguishable 'turn-on' fluorescence response: multi-stimuli responsive quinoline derivatives in action.

We have successfully synthesized quinoline derivatives that exhibit easy scalability and responsiveness to multiple stimuli. These derivatives are capable of forming self-assembled nanoscopic aggregates in an aqueous medium. Consequently, when placed in an aqueous environment, we observe dual fluorescence originating from both twisted intramolecular charge transfer and aggregation-induced emission. The introduction of nerve gas agents, such as diethyl chlorophosphate (DClP) or diethylcyanophosphate (DCNP), to the probe molecules facilitates the charge-transfer process, resulting in a red-shift in absorption maxima. Notably, when operating in fluorescence mode, both of these analytes produce distinct output signals, making them easily distinguishable. DCNP generates a blue fluorescence, while the addition of DClP yields cyan fluorescence. Our mechanistic investigation reveals that the initial step involves phosphorylation of the quinoline nitrogen end. However, in the case of DCNP, the released cyanide ion subsequently attacks the carbonyl carbon centre, forming a cyanohydrin derivative. The response to these target analytes appears to be influenced by the nucleophilicity of the quinoline nitrogen end and the electrophilic nature of the carbonyl unit.

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation.

A phosphine-free, efficient protocol for aminocarbonylation and carbonylative Suzuki-Miyaura coupling has been developed using a novel palladium complex, [PdII(DMAP)2(OAc)2]. The complex was successfully synthesized using a stoichiometric reaction between PdII(OAc)2 and DMAP in acetone at room temperature and characterized using single-crystal X-ray analysis. Only 5 mol % catalyst loading was sufficient for effective carbonylative transformations. "Chloroform-COware" chemistry was utilized for safe and facile insertion of the carbonyl unit using chloroform as an inexpensive CO source in a two-chamber setup. Various value-added pharmaceutically relevant compounds such as CX-516, CX-546, and farampator were synthesized using the technique. Furthermore, the commercially designed COware was engineered to COware-RB setup for sequential one-pot synthesis of indenoisoquinolines (topoisomerase I inhibitors).

Deoxygenation of Oxiranes by λ3 σ3 -Phosphorus Reagents: A Computational, Mechanistic, and Stereochemical Study.

The deoxygenation of parent and substituted oxiranes by λ3 σ3 -phosphorus reagents has been explored in detail, therefore unveiling mechanistic aspects as well as regio- and stereochemical consequences. Attack to a ring C atom is almost always preferred over one-step deoxygenation by direct P-to-O attack. In most cases a carbene transfer occurs as first step, leading to a phosphorane and a carbonyl unit that thereafter react in the usual Wittig fashion via the corresponding λ5 σ5 -1,2-oxaphosphetane intermediate. Betaines rarely constitute true minima after the first C-attack to oxiranes, at least in the gas-phase. Use of the heavier derivatives AsMe3 and SbMe3 as oxirane deoxygenating reagents was also mechanistically studied. The thermodynamic tendency of λ3 σ3 -phosphorus reagents to act as oxygen (O-attack) or carbene acceptors (C-attack) was theoretically studied by means of the thermodynamic oxygen-transfer potential (TOP) and the newly defined thermodynamic carbene-transfer potential (TCP) parameters, that were explored in a wider context together with many other acceptor centres.

Visible-Light-Induced Desaturative β-Alkoxyoxalylation of N-Aryl Cyclic Amines with Difluoromethyl Bromides and H2O Via a Triple Cleavage Process.

A visible-light-driven desaturative β-alkoxyoxalyation of N-aryl cyclic amines with difluoromethyl bromides and H2O has been reported. This tandem reaction is triggered by homolysis of the C-Br bond to produce the difuoroalkyl radical, which undergoes the subsequent defluorinated β-alkoxyoxalylation cascades to afford a wide range of β-ketoester/ketoamides substituted enamines. The prominent feature of this reaction contains photocatalyst-free, transition-metal free, and mild conditions. The 18O labeling experiment disclosed that H2O is the oxygen source of the carbonyl unit.

Palladium-Catalyzed Carbonylative Synthesis of Polycyclic 3,4-Dihydroquinolin-2(1H)-one Scaffolds Containing Perfluoroalkyl and Carbonyl Units.

A palladium-catalyzed one-pot two-step radical mediated carbonylative cyclization of 1,7-enynes with perfluoroalkyl iodides and Mo(CO)6 has been developed for the construction of polycyclic 3,4-dihydroquinolin-2(1H)-one scaffolds. This method realizes a facile synthesis of various polycyclic 3,4-dihydroquinolin-2(1H)-one derivatives containing perfluoroalkyl and carbonyl units in high yields. Moreover, modifications of several bioactive molecules were demonstrated using this protocol.

A Facile synthesis of Biaryl ketones in recyclable system: Triazenes as new coupling partners in the carbonylative Suzuki and Hiyama cross‐coupling reactions using NFSac as CO source

AbstractPalladium‐catalyzed carbonylation reactions aid as potent tools for the insertion of carbonyl unit(s) in a wide array of molecules possessing vast number of applications in multiple domains. An efficient and facile protocol has been reported for the carbonylative Suzuki (CO−S) and carbonylative Hiyama (CO−H) coupling of aryl triazenes using phenyl boronic acid and triethoxy(phenyl)silane respectively via a Pd‐catalysis in combination with Ionic liquids (ILs). Four different ILs have been employed as solvent/reagent/promotor(s) to afford the targeted products in reasonably good yields. As per the predictive mechanism, an in situ generated N‐Heterocarbene‐Ionicliquid‐Palladium (NHC‐IL‐Pd) species serve as a regenerative catalyst while the N‐formyl saccharin (NFSac), a non‐hazardous and commercially available crystalline compound was used as carbon monoxide (CO) surrogate playing important roles to accomplish the desired products in good yields.

Asymmetric Synthesis of Remotely Chiral Naphthols and Naphthylamines via Naphthoquinone Methides.

Quinone methides are well-established intermediates in asymmetric synthesis. In contrast, their extended analogues with the carbonyl and methide units distributed across two different rings have not been exploited in asymmetric synthesis. Herein, we achieved the first asymmetric process involving such intermediates. Specifically, the use of suitable chiral phosphoric acids enabled in situ generation of 2-naphthoquinone 8-methides and the corresponding aza counterparts for mild one-pot asymmetric nucleophilic addition. These processes provided rapid access to a wide range of previously less accessible remotely chiral naphthols and naphthylamines with both high efficiency and excellent enantioselectivity. Control experiment and DFT calculations provided important insights into the reaction mechanism, which likely involves two phosphoric acid molecules in the enantiodetermining transition states. This work serves as a proof of concept for the exploitation of new types of extended quinone methides as versatile intermediates for asymmetric synthesis, thus providing a new platform for the efficient construction of remote benzylic stereogenic centers of aromatic compounds.

Unveiling the gemcitabine drug complexation with cucurbit[n]urils (n = 6–8): a computational analysis

In this work, we have investigated the complex formation capability of gemcitabine drug with host cucurbit[n]urils, Q[n] (n = 6, 7, and 8) using density functional theory (DFT). The DFT studies demonstrate that the most stable configuration is a fully encapsulated complex. In the encapsulated gemcitabine@Q[6] and gemcitabine@Q[7] complexes, the gemcitabine amino -NH2 and the alcoholic groups bond with the carbonyl units of Q[n]. The addition of sodium ions leads to the partial exclusion of the gemcitabine molecule and the sodium atoms lie close to the carbonyl portal of Q[7]. Thermodynamic parameters computed for the complexation process exhibit high negative Gibbs free energy change, implying that the encapsulation process is spontaneous and is an enthalpy-driven process. Frontier molecular orbitals are located mainly on the gemcitabine uracil ring, before and after encapsulation, indicating that the encapsulation occurs by pure physical adsorption. Quantitative molecular electrostatic potentials demonstrate a shift in electron density during the complex formation and are more pronounced in gemcitabine@Q[7]. Atoms-in-molecule (AIM) topological analysis illustrate that these complexes are stabilized by various non-covalent interactions including hydrogen bonding (HBs) and C···F interactions. The reduced density gradient (RDG) graph exhibits the presence of strong HBs and weak van der Waals interactions and the presence of steric repulsion. The isosurface non-covalent interactions (NCI) diagram shows predominant steric interaction in the gemcitabine@Q[6] complex. The NCI isosurface for gemcitabine encapsulated complexes with Q[7] and Q[8] host displays that the green patches are uniformly distributed in all directions. Finally, EDA results demonstrate Pauling’s repulsive energy is predominant in gemcitabine@Q[6] complex, while the orbital and dispersion energies stabilize the gemcitabine@Q[7] complex.