Defective Potassium Poly(Heptazine Imide) Preventing Spin Delocalization and Hole Transfer Deactivation for Efficient Solar Energy Conversion and Storage.

Anti-site defective potassium poly(heptazine imide) (KPHI) with the central nitrogen atoms partially replaced by graphitic carbon atoms in the flawed heptazine rings is prepared by direct ionothermal treatment of the rationally designed supramolecular complex in KSCN salt molten. Compared to the KPHIs without the anti-site defect, the anti-site defective KPHI demonstrates significantly improved photocatalytic and dark photocatalytic performances for H2 evolution reaction (HER). In the presence of the hole scavenger, the anti-site defective KPHI exhibits superior photocatalytic stability for HER lasting 20 h, whereas the deactivation is observed from the ordinary KHPIs after 3 h HER. Moreover, the H2 yield in the dark by the stored photoelectrons in the anti-site defective KPHI increases by more than an order of magnitude. Density functional theory calculations reveal that the anti-site defective unit in KPHI not only prevents spin delocalization but also inhibits the deactivation of hole transfer, which are beneficial to photoelectron storage and photocatalytic activity. The findings in this study provide insight into the photophysical and catalytic properties of KPHI, which conclude a strategy to improve the performances for solar energy conversion and storage by incorporating intrinsic anti-site defects in KPHI.

Solvated Electrons Generated on the Surface of Na-SPHI for Boosting Visible Light Photocatalytic Hydrogen Evolution with Ultra-High AQE.

Enhancing the utilization of visible-light-active semiconductors with an excellent apparent quantum efficiency (AQE) remains a significant and challenging goal in the realm of photocatalytic water splitting. In this study, a fully condensed sulfur-doped poly(heptazine imide) metalized with Na (Na-SPHI) is synthesized by an ionothermal method by using eutectic NaCl/LiCl mixture as the ionic solvent. Comprehensive characterizations of the obtained Na-SPHI reveal several advantageous features, including heightened light absorption, facilitated exciton dissociation, and expedited charge transfer. More importantly, solvated electron, powerful reducing agents, can be generated on the surface of Na-SPHI upon irradiation with visible light. Benefiting from above advantage, the Na-SPHI exhibits an excellent H2 evolution rate of 571.8 µmol·h-1 under visible light illumination and a super-high AQE of 61.7% at 420 nm. This research emphasizes the significance of the solvated electron on the surface of photocatalyst in overcoming the challenges associated with visible light-driven photocatalysis, showcasing its potential application in photocatalytic water splitting.

Robust, Self-Healing, and Multi-Use Poly(Urethane-Urea-Imide) Elastomer as a Durable Adhesive for Thermal Interface Materials.

Currently, research on thermal interface materials (TIMs) is primarily focused on enhancing thermal conductivity. However, strong adhesion and multifunctionality are also important characteristics for TIMs when pursing more stable interface heat conduction. Herein, a novel poly(urethane-urea-imide) (PUUI) elastomer containing abundant dynamic hydrogen bonds network and reversible disulfide linkages is successfully synthesized for application as a TIM matrix. The PUUI can self-adapt to the metal substrate surface at moderate temperatures (80 °C) and demonstrates a high adhesion strength of up to 7.39 MPa on aluminum substrates attributed its noncovalent interactions and strong intrinsic cohesion. Additionally, the PUUI displays efficient self-healing capability, which can restore 94% of its original mechanical properties after self-healing for 6 h at room temperature. Furthermore, PUUI composited with aluminum nitride and liquid metal hybrid fillers demonstrates a high thermal conductivity of 3.87 W m-1 K-1 while maintaining remarkable self-healing capability and adhesion. When used as an adhesive-type TIM, it achieves a low thermal contact resistance of 22.1 mm2 K W-1 at zero pressure, only 16.7% of that of commercial thermal pads. This study is expected to break the current research paradigm of TIMs and offers new insights for the development of advanced, reliable, and sustainable TIMs.

Driving Triplet State Population in Benzothioxanthene Imide Dyes: Let's twist!

Controlling the formation of photoexcited triplet states is critical for many (photo)chemical and physical applications. Here, we demonstrate that a permanent out-of-plane distortion of the benzothioxanthene imide (BTI) dye promotes intersystem crossing by increasing spin-orbit coupling. This manipulation was achieved through a subtle chemical modification, specifically the bay-area methylation. Consequently, this simple yet efficient approach expands the catalog of known molecular engineering strategies for synthesizing heavy atom-free, dual redox-active, yet still emissive and synthetically accessible photosensitizers.

A Sodium Bis(fluorosulfonyl)imide (NaFSI)-based Multifunctional Electrolyte Stabilizes the Performance of NaNi1/3Fe1/3Mn1/3O2/hard Carbon Sodium-ion Batteries.

A sodium bis(fluorosulfonyl)imide (NaFSI)-based multifunctional electrolyte is developed by partially replacing NaPF6 salt in the electrolyte to improve the wide temperature range working capability of NaNi1/3Fe1/3Mn1/3O2/hard carbon (NNFM111/HC) sodium-ion batteries (SIBs). The capacity retention of the SIBs with NaFSI-NaPF6 dual salt electrolyte increases from 47.2 % to 75.5 % after 250 cycles at 25 °C, and from 51.0 % to 82.3 % after 80 cycles at 45 °C, and the 1 C discharge capacity retention at the low temperature of -20 °C also increases 26.8 %. In the single salt system, NaPF6 effectively passivate the aluminum foil and NaFSI passivate the electrode/electrolyte interface. The synergistic effect of NaPF6 and NaFSI greatly improves the battery performance in a wide temperature range. This NaFSI-based dual salt electrolyte also effectively overcomes the flaws when the SIBs using NaFSI or NaPF6 independently, and makes it more suitable for SIBs, indicating promising prospects in the commercial application of NNFM111/HC SIBs.

n-Bu4NI/K2S2O8 Mediated Csp2-Csp2 Bond Cleavage - Transformylation from p-Anisaldehyde to Primary Amides.

n-Bu4NI/K2S2O8 mediated transformylation from p-anisaldehyde to primary amides is reported. The mechanistic studies suggest the reaction occurs via a single electron transfer pathway. Based on the DFT electronic structure calculations of various reaction pathways, the most plausible mechanism involves the formation of a phenyl radical cation and an arenium ion as the key intermediates. It represents the first example where p-anisaldehyde is employed as a formyl source via a non-metal mediated Csp2-Csp2 bond cleavage.

Effect of 1,4-Dioxane Solvent on ß-Glucuronidation Using Methyl 1,2,3,4-Tetra-O-acetyl-ß-D-glucuronate as the Glycosyl Donor.

A facile and selective ß-D-glucuronidation of alcohols, such as (-)-menthol, cholestanol, (+)- and (-)-borneols, and 2-adamantanol, using commercially available methyl 1,2,3,4-tetra-O-acetyl-ß-D-glucuronate as the glycosyl donor and trimethylsilyl bis(trifluoromethanesulfonyl)imide (Tf2NTMS) (0.5 equivalent) as the activator in 1,4-dioxane at 60 °C gave products in moderate yields. The addition of MS4A increased the ß : α ratios of D-glucuronides when cholestanol, (+)-borneol, and 2-adamantanol were used as the acceptor substrate.

Engineering Polyheptazine and Polytriazine Imides for Photocatalysis.

As organic semiconductor materials gain increasing prominence in the realm of photocatalysis, two carbon-nitrogen materials, poly (heptazine imide) (PHI) and poly (triazine imide) (PTI), have garnered extensive attention and applications owing to their unique structure properties. This review elaborates on the distinctive physical and chemical features of PHI and PTI, emphasizing their formation mechanisms and the ensuing properties. Furthermore, it elucidates the intricate correlation between the energy band structures and various photocatalytic reactions. Additionally, the review outlines the primary synthetic strategies for constructing PHI and PTI, along with characterization techniques for their identification. It also summarizes the primary strategies for enhancing the photocatalytic performance of PHI and PTI, whose advantages in various photocatalytic applications are discussed. Finally, it highlights the promising prospects and challenges pertaining to PHI and PTI as photocatalysts.

Multi-Selenophene Incorporated Thiazole Imide-Based n-Type Polymers for High-Performance Organic Thermoelectrics.

Developing polymers with high electrical conductivity (σ) after n-doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide-based n-type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene-free analogue. Consequently, polymer PDTzSI-Se with the highest selenophene content achieves a champion σ of 164.0 S cm-1 and a power factor of 49.0 µW m-1 K-2 in the series when applied in OTEs after n-doping. The σ value is the highest one for n-type donor-acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high-performance n-type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n-type polymers with high backbone coplanarity, deep-lying LUMO and enhanced mobility/conductivity.

Achieving Record External Quantum Efficiency of 11.5 % in Solution-Processable Deep-Blue Organic Light-Emitting Diodes Utilizing Hot Exciton Mechanism.

High performance solution-processable deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition display. Although, deep-blue materials with hybridized local and charge-transfer (HLCT) excited-state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution-processing technique. Herein, four novel deep-blue solution-processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation-caused quenching effect due to the weak electron-withdrawing property as well as steric hindrance. The corresponding solution-processable organic light-emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state-of-the-art device performance among the solution-processable blue OLEDs based on the "hot exciton" mechanism. This simple strategy opens up a new avenue for designing highly efficient solution-processable deep-blue organic luminescent materials.

Functionalized Phenanthrene Imide-Based Polymers for n-Type Organic Thin-Film Transistors.

High-performing n-type polymers are crucial for the advance of organic electronics field, however strong electron-deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide-functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π-conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high-performance n-type polymers. Among the PAHs, phenanthrene (PhA) features a well-delocalized aromatic π-system with multiple modifiable active sites . However, the PhA-based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene-modified CPCNI exhibits a well stabilized LUMO energy level (-3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI-Tz and PCPCNI-Tz were developed. Applied to organic thin-film transistors, owing to the strong electron-deficiency of CPCNI, polymer PCPCNI-Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI-Tz. This work affords two structurally novel electron-deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron-withdrawing groups for devising n-type polymers.

Development of On-DNA Cyclic Imide Synthesis for DNA Encoded Library Construction.

Here, we describe a novel method for the on-DNA synthesis of cyclic imides, an important class of molecules that includes several well-known medications. Significantly, the new method enabled on-DNA synthesis under mild conditions with high conversions and a broad functional group tolerance, utilizing ubiquitous bifunctional amines and bis-carboxylic acid, or alkyl halides, and therefore served as the linchpin for DNA encoded library (DEL) synthesis. The mechanism study of off-DNA and on-DNA chemical transformations revealed unique insights in contrast to conventional chemical transformation.

Aluminium and Gallium Silylimides as Nitride Sources.

Terminal aluminium and gallium imides of the type K[(NON)M(NR)], bearing heteroatom substituents at R, have been synthesised via reactions of anionic aluminium(I) and gallium(I) reagents with silyl and boryl azides (NON=4,5-bis(2,6-diisopropyl-anilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene). These systems vary significantly in their lability in solution: the N(Sii Pr3 ) and N(Boryl) complexes are very labile, on account of the high basicity at nitrogen. Phenylsilylimido derivatives provide greater stabilization through the π-acceptor capabilities of the SiR3 group. K[(NON)AlN(Sit BuPh2 )] offers a workable compromise between stability and solubility, and has been completely characterized by spectroscopic, analytical and crystallographic methods. The silylimide species examined feature minimal π-bonding between the imide ligand and aluminium/gallium, with the HOMO and HOMO-1 orbitals effectively comprising orthogonal lone pairs centred at N. Reactivity-wise, both aluminium and gallium silylimides can act as viable sources of nitride, [N]3- , with systems derived from either metal reacting with CO to afford cyanide complexes. By contrast, only the gallium system K[(NON)Ga{N(SiPh3 )}] is capable of effecting a similar transformation with N2 O to yield azide, N3 - , via formal oxide/nitride metathesis. The aluminium systems instead generate RN3 via transfer of the imide fragment [RN]2- .

An Aluminium Imide as a Transfer Agent for the [NR]2- Function via Metathesis Chemistry.

The reactions of a terminal aluminium imide with a range of oxygen-containing substrates have been probed with a view to developing its use as a novel main group transfer agent for the [NR]2- fragment. We demonstrate transfer of the imide moiety to [N2 ], [CO] and [Ph(H)C] units driven thermodynamically by Al-O bond formation. N2 O reacts rapidly to generate the organoazide DippN3 (Dipp=2,6-i Pr2 C6 H3 ), while CO2 (under dilute reaction conditions) yields the corresponding isocyanate, DippNCO. Mechanistic studies, using both experimental and quantum chemical techniques, identify a carbamate complex K2 [(NON)Al-{κ2 -(N,O)-N(Dipp)CO2 }]2 (formed via [2+2] cycloaddition) as an intermediate in the formation of DippNCO, and also in an alternative reaction leading to the generation of the amino-dicarboxylate complex K2 [(NON)Al{κ2 -(O,O')-(O2 C)2 N-(Dipp)}] (via the take-up of a second equivalent of CO2 ). In the case of benzaldehyde, a similar [2+2] cycloaddition process generates the metallacyclic hemi-aminal complex, Kn [(NON)Al{κ2 -(N,O)-(N(Dipp)C(Ph)(H)O}]n . Extrusion of the imine, PhC(H)NDipp, via cyclo-reversion is disfavoured thermally, due to the high energy of the putative aluminium oxide co-product, K2 [(NON)Al(O)]2 . However, addition of CO2 allows the imine to be released, driven by the formation of the thermodynamically more stable aluminium carbonate co-product, K2 [(NON)Al(κ2 -(O,O')-CO3 )]2 .

Base-Stabilized Phosphinidene Oxide, Imide and Sulfide.

Oxidation of a base-stabilized phosphinidene (κ2 -NNP)P (12, NNP=phosphinoamidinate) with N2 O afforded a labile phosphinidene oxide (κ2 -NNP)P=O (16) which was characterized by NMR spectroscopy. Further oxidation of 16 by N2 O or reaction of 12 with two equivalents of pyridine oxide afforded the isolable dioxide (κ2 -NNP)PO2 which was characterized by NMR and SC XRD. Trapping of 16 with tolyl isocyanate resulted in P=O/N=C metathesis, eventually affording a urea-ligated phosphine (κ1 -NNP)P(NTol)2 C=O (17) The mechanism of this reaction was elucidated by DFT calculations. Reactions of phosphinidene 12 with azides generated transient imines (NNP)P=NR, which in the case of R=Tol underwent cycloaddition with tolyl Isocyanate to afford the urea product 17, and in the case of R=SiMe3 reacts with N3 SiMe3 via the addition of N-Si across the P=N bond affording, after the extrusion of dinitrogen, a P,N-heterocyclic compound. Both products of the reactions with azides have been fully characterized, both in solution and the solid-state. Finally, reaction of phosphinidene 12 with one equivalent of sulfur resulted in the isolation of the base-stabilized phosphinidene sulfide (κ2 -NNP)P=S that has also been fully characterized.

Novel, thalidomide-like, non-cereblon binding drug tetrafluorobornylphthalimide mitigates inflammation and brain injury.

BACKGROUND: Quelling microglial-induced excessive neuroinflammation is a potential treatment strategy across neurological disorders, including traumatic brain injury (TBI), and can be achieved by thalidomide-like drugs albeit this approved drug class is compromised by potential teratogenicity. Tetrafluorobornylphthalimide (TFBP) and tetrafluoronorbornylphthalimide (TFNBP) were generated to retain the core phthalimide structure of thalidomide immunomodulatory imide drug (IMiD) class. However, the classical glutarimide ring was replaced by a bridged ring structure. TFBP/TFNBP were hence designed to retain beneficial anti-inflammatory properties of IMiDs but, importantly, hinder cereblon binding that underlies the adverse action of thalidomide-like drugs. METHODS: TFBP/TFNBP were synthesized and evaluated for cereblon binding and anti-inflammatory actions in human and rodent cell cultures. Teratogenic potential was assessed in chicken embryos, and in vivo anti-inflammatory actions in rodents challenged with either lipopolysaccharide (LPS) or controlled cortical impact (CCI) moderate traumatic brain injury (TBI). Molecular modeling was performed to provide insight into drug/cereblon binding interactions. RESULTS: TFBP/TFNBP reduced markers of inflammation in mouse macrophage-like RAW264.7 cell cultures and in rodents challenged with LPS, lowering proinflammatory cytokines. Binding studies demonstrated minimal interaction with cereblon, with no resulting degradation of teratogenicity-associated transcription factor SALL4 or of teratogenicity in chicken embryo assays. To evaluate the biological relevance of its anti-inflammatory actions, two doses of TFBP were administered to mice at 1 and 24 h post-injury following CCI TBI. Compared to vehicle treatment, TFBP reduced TBI lesion size together with TBI-induction of an activated microglial phenotype, as evaluated by immunohistochemistry 2-weeks post-injury. Behavioral evaluations at 1- and 2-weeks post-injury demonstrated TFBP provided more rapid recovery of TBI-induced motor coordination and balance impairments, versus vehicle treated mice. CONCLUSION: TFBP and TFNBP represent a new class of thalidomide-like IMiDs that lower proinflammatory cytokine generation but lack binding to cereblon, the main teratogenicity-associated mechanism. This aspect makes TFBP and TFNBP potentially safer than classic IMiDs for clinical use. TFBP provides a strategy to mitigate excessive neuroinflammation associated with moderate severity TBI to, thereby, improve behavioral outcome measures and warrants further investigation in neurological disorders involving a neuroinflammatory component.

Further Insight into Extractable (Organo)fluorine Mass Balance Analysis of Tap Water from Shanghai, China.

The ubiquitous occurrence of per- and polyfluoroalkyl substances (PFAS) and the detection of unexplained extractable organofluorine (EOF) in drinking water have raised growing concerns. A recent study reported the detection of inorganic fluorinated anions in German river systems, and therefore, in some samples, EOF may include some inorganic fluorinated anions. Thus, it might be more appropriate to use the term "extractable fluorine (EF) analysis" instead of the term EOF analysis. In this study, tap water samples (n = 39) from Shanghai were collected to assess the levels of EF/EOF, 35 target PFAS, two inorganic fluorinated anions (tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-)), and novel PFAS through suspect screening and potential oxidizable precursors through oxidative conversion. The results showed that ultra-short PFAS were the largest contributors to target PFAS, accounting for up to 97% of ΣPFAS. To the best of our knowledge, this was the first time that bis(trifluoromethanesulfonyl)imide (NTf2) was reported in drinking water from China, and p-perfluorous nonenoxybenzenesulfonate (OBS) was also identified through suspect screening. Small amounts of precursors that can be oxidatively converted to PFCAs were noted after oxidative conversion. EF mass balance analysis revealed that target PFAS could only explain less than 36% of EF. However, the amounts of unexplained extractable fluorine were greatly reduced when BF4- and PF6- were included. These compounds further explained more than 44% of the EF, indicating the role of inorganic fluorinated anions in the mass balance analysis.

Amphoteric dissolution of two-dimensional polytriazine imide carbon nitrides in water.

Crystalline two-dimensional carbon nitrides with polytriazine imide (PTI) structure are shown to act amphoterically, buffering both HCl and NaOH aqueous solutions, resulting in charged PTI layers that dissolve spontaneously in their aqueous media, particularly for the alkaline solutions. This provides a low energy, green route to their scalable solution processing. Protonation in acid is shown to occur at pyridinic nitrogens, stabilized by adjacent triazines, whereas deprotonation in base occurs primarily at basal plane NH bridges, although NH2 edge deprotonation is competitive. We conclude that mildly acidic or basic pHs are necessary to provide sufficient net charge on the nanosheets to promote dissolution, while avoiding high ion concentrations which screen the repulsion of like-charged PTI sheets in solution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Facile Preparation of L-Iduronic Acid and α-L-Iduronidation Using Methyl 1,2,3,4-Tetra-O-acetyl-α-L-iduronate as Glycosyl Donor.

Methyl 1,2,3,4-tetra-O-acetyl-α-L-iduronate was prepared from methyl 1,2,3,4-tetra-O-ß-D-glucuronate in two steps: Ferrier's photobromination and subsequent radical reduction with tris(trimethylsilyl)silane. The obtained methyl 1,2,3,4-tetra-O-acetyl-α-L-iduronate was a good glycosyl donor for the L-iduronidation when bis(trifluoromethanesulfonic)imide was employed as the activator. The reaction afforded the α-isomer as the major product, the configuration of which is the same as that of the L-iduronic acid unit in heparin and heparan sulfate.

Bottom-up Synthesis of Single-Crystalline Poly (Triazine Imide) Nanosheets for Photocatalytic Overall Water Splitting.

Poly (triazine imide) (PTI/Li+ Cl- ), one of the crystalline versions of polymeric carbon nitrides, holds great promise for photocatalytic overall water splitting. In principle, the photocatalytic activity of PTI/Li+ Cl- is closely related to the morphology, which could be reasonably tailored by the modulation of the polycondensation process. Herein, we demonstrate that the hexagonal prisms of PTI/Li+ Cl- could be converted to hexagonal nanosheets by adjusting the binary eutectic salts from LiCl/KCl or NaCl/LiCl to ternary LiCl/KCl/NaCl. Results reveal that the extension of in-plane conjugation is preferred, when the polymerisation was performed in the presence of ternary eutectic salts. The hexagonal nanosheets bears longer lifetimes of charge carriers than that of hexagonal prisms due to lower intensity of structure defects and shorter hopping distance of charge carriers along the stacking direction of triazine nanosheets. The optimized hexagonal nanosheets exhibits a record apparent quantum yield value of 25 % (λ=365 nm) for solar hydrogen production by one-step excitation overall water splitting.