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The zinc ion is used as a catalyst to effectively replace the traditional copper ion catalyst to participate in the redox reaction of hydrazine hydrate and hydrogen peroxide to generate diimide to selectively hydrogenate the carbon–carbon double bonds in the nitrile butadiene rubber (NBR) latex to prepare hydrogenated NBR (HNBR). The optimized zinc ion catalytic hydrogenation system was obtained through orthogonal design experiment screening. Among them, the hydrogenation of NBR latex with zinc chloride as a catalyst can obtain HNBR-ZnCl2 products with high hydrogenation degree (90.58%), high thermal stability, and high regularity. Using zinc ions as a catalyst instead of copper ions can effectively improve the damage of copper ions remaining in the hydrogenated product on the thermal-oxidative aging resistance performance of rubber. Compared with HNBR hydrogenated by copper ions, HNBR hydrogenated by zinc ion catalysts has better thermal-oxidative aging resistance performance. [ABSTRACT FROM AUTHOR]

A new 'Off–On' system designed and synthesised by functionalisation of a naphthalene diimide (NDI) core with dimethylamine produces 4,9‐bis(dimethylamino)‐2,7‐dioctylbenzo[lmn][3,8]‐phenanthroline‐1,3,6,8‐(2H,7H)‐tetraone, abbreviated as DDPT (1). DDPT 1 was synthesised using a simple strategy, namely aromatic nucleophilic substitution using Br2‐NDI with dimethylamine at 110 °C. DDPT was characterized by 1H and 13C NMR spectroscopy, ESI mass spectrometry and elemental analysis. DDPT 1 was then used for optical studies through protonation of its dimethylamine core with trifluoroacetic acid (TFA), blue‐shifting the absorption band from 600 nm to 545 nm in solution. Interestingly, the fluorescence of DDPT 1 is weak in solution with a quantum yield Φ=0.09, which is significantly enhanced to Φ=0.78 upon addition of TFA. The limit of detection (LOD) was determined to 2.77 nm. Furthermore, DDPT 1 can be used for naked eyed detection not only under UV light (365 nm) but also using visible light, as clear changes can be clearly seen upon addition of TFA. The binding constant of DDPT was calculated to 2.1×10−3 m−1. Importantly, DDPT 1 showed reversible switching by alternative addition of acid (TFA) and base (triethylamine) without loss of activity. Immobilised on paper, DDPT 1 can be used for strip‐test sensing in which the colour changes from blue to reddish when expose to TFA vapours and reverse in the presence of triethylamine vapours. [ABSTRACT FROM AUTHOR]

A strong σ-donating cyclic (alkyl)(amino) carbene (cAAC) triggers rearrangement of the silyl(aryl) amido ligand -N(SiMe3)Dipp (Dipp = 2,6-diisopropylphenyl) in the coordination sphere of titanium(III) to afford a novel zwitterionic titanium imido complex with a TiCH2SiMe2[cAAC] linkage. Reduction of this species produces a new DippN=Ti imido complex containing a cAAC-centered radical species, characterized by single crystal diffraction analysis and electron paramagnetic resonance spectroscopy.

3,4,9,10-perylene tetracarboxylic diimide molecules were evaporated onto a Ag/Si(111)- √3 × √3 surface and studied by scanning tunneling microscopy/spectroscopy and low energy electron diffraction (LEED). The growth mode was characterized as layer-by-layer growth with a single molecular unit cell in a short range order. The growth of the first two monolayers involves a molecule/substrate superstructure and a molecule/molecule superstructure. At higher coverages, the molecules in each layer were found to align so that unit cells are on top of each other. The experimentally obtained LEED pattern is described as a combination of patterns from the molecular unit cell and the molecule/substrate superstructure. The electronic structure was found to be strongly dependent on the film thickness for the first few layers: Several extra states are found at low coverages compared to higher coverages resulting in a very small pseudo gap of 0.9 eV for the first layer, which widens up to 4.0 eV for thicker films. [ABSTRACT FROM AUTHOR]

Despite the innumerous papers regarding the study of the ionic liquids as a potential candidate for CO2 capture, many details concerning the structure and dynamics of CO2 in the system are still to be revealed, i.e., the correlation between the local environment structure and the dynamic properties of the substance. This present work relied on the performance of molecular dynamics both for the neat [C2mim][Tf2N] and [C2mim][Tf2N]/CO2 mixtures in an attempt to elucidate the local environment of CO2 and their effects on the dynamic properties of [C2mim][Tf2N]. A slight change in the orientation of the cation and anion could be observed, which was correlated to the cation and anion moving away from each other in order to receive the carbon dioxide. The gas molecules pushed both the cation and the anion away to create sufficient void to its accommodation. The diffusion coefficient of [C2mim]+ is higher than [Tf2N]- regardless the increase of the CO2 concentration. The addition of CO2 in the ionic liquid has shown an increase of 4-5 times for the diffusivity of ions, which was related to the decrease of cation-anion interaction strength. The transport properties' results showed that the addition of CO2 in the ionic liquid generates the fluidization of the system, decreasing the viscosity as a consequence of the local environment structure changing. Likewise, the effect of the type of anion and cation on the system properties was studied considering [Ac]- and [BMpyr]+ ions, showing large effects by the change of anion to [Ac]- which rise from the strong [C2mim]+-[Ac]- interaction, which conditions the solvation of ions by CO2 molecules. [ABSTRACT FROM AUTHOR]

• Mesogenic di(decyloxy)-substituted triphenylene 2,3,6,7-tetracarboxyldiimides and triphenylene monoimide diesters were synthesized for the first time. • Having good solubility in common organic solvents and excellent thermally stability. • Different imide substituents have a significant effect on the self-assembly both in solution and the liquid-crystalline state. • One diimide has an unusually large hexagonal columnar mesophase range of 292 °C from 7 °C up to 299 °C. Unlike the well-explored perylene diimides and naphthalene diimides, the synthesis and characterization of triphenylene diimides have not been reported to date. In this study, several di(decyloxy)-substituted triphenylene 2,3,6,7-tetracarboxyldiimides with various imide substituents were synthesized and comprehensively analyzed for their photochemical properties and mesophase behavior. It was observed that different imide substituents significantly affect self-assembly in both solution and the liquid-crystalline state. Specifically, diimide 2 – 1 , with two n-octyl chains at the imide nitrogens, exhibits a tendency to self-assembly at relatively high concentrations in CDCl 3 and displays a hexagonal columnar (Col h) phase near room temperature. Remarkably, its isomer, diimide 2 – 2 , with two branched 2-ethylhexyl chains, exhibits an enatiotropic Col h phase with an unusually large range of 292 °C, extending from 7 °C to 299 °C. Furthermore, the study also reports two triphenylene monoimide diesters as room temperature liquid crystals, each composed of one imide, two alkoxycarbonyl, and two alkoxy side chains. These findings not only enrich the diversity of aromatic diimides but also highlight the potential applications of these novel diimides in the field of liquid crystals. [ABSTRACT FROM AUTHOR]

[Display omitted] • • A perylene diimide derivative based probe P1 with hydroxyl and bipyridine-like groups at bay region has been developed as a bifunctional fluorescent probe. • • The fluorescence of the probe can be quenched by F- while enhanced by Cu2+. The detection limits were 0.17 μM and 0.21 μM, respectively. • • The probe has potential applications for the detection of F- and Cu2+ in the environmental and living cells. • • This method has the advantages of high selectivity, simplicity, economy, and rapidity. A bifunctional fluorescent probe P1 based on perylene diimide derivative (PDI) was developed, demonstrating high sensitivity and selectivity for the rapid detection of fluoride (F-) and copper (Cu2+). The fluorescence of P1 was quenched upon interaction with F- and enhanced upon interaction with Cu2+. The concentration ranges for fluorescent detection of F- and Cu2+ are 0 ∼ 4 × 10-5 M and 0 ∼ 2.4 × 10-5 M, respectively. The stoichiometry of the complex formed between Cu2+ and P1 or F− and P1 was 1:1. The probe displays detection limits of 0.16 and 0.21 μM and binding constants (K sv) of 3.92 × 104 and 1.72 × 104 M−1 for the detection of F- and Cu2+, respectively. The sensing mechanism and binding mode of P1 with F- and Cu2+ were investigated. The fluorescence quenching/enhancement of P1 was controlled by a photoinduced electron-transfer (PET) process. Furthermore, the ability of the probe to detect intracellular F- and Cu2+ was assessed using cell imaging techniques. [ABSTRACT FROM AUTHOR]

[Display omitted] • Single-step diimide reduction of saturated 6-(4′-aryloxy phenyl) vinyl 1,2,4-trioxanes has been reported. • Antimalarial activities of the synthesized compounds were evaluated by oral route against multi-drug resistant Plasmodium yoelii nigeriensis. • Cyclopentane-based trioxanes provided best protection to infected mice amongst all. • Trioxane 12b1 is four-fold active than β-arteether via oral route. Novel saturated 6-(4′-aryloxy phenyl) vinyl 1,2,4-trioxanes 12a(1 – 3)–12d(1 – 3) and 13a(1 – 3)–13d(1 – 3) have been designed and synthesized, in one single step from diimide reduction of 11a(1 – 3)–11d(1 – 3). All the newly synthesized trioxanes were evaluated for their antimalarial activity against multi-drug resistant Plasmodium yoelii nigeriensis via oral route. Cyclopentane-based trioxanes 12b1, 12c1 and 12d1 , provided 100 % protection to the infected mice at 24 mg/kg × 4 days. The most active compound of the series, trioxane 12b1 , provided 100 % protection even at 12 mg/kg × 4 days and 60 % protection at 6 mg/kg × 4 days. The currently used drug, β-arteether provides only 20 % protection at 24 mg/kg × 4 days. [ABSTRACT FROM AUTHOR]

• Unsymmetrical perylene diimide derivative have been synthesized. • In non-polar solvent systems, they self-assembled into ribbon-like nanostructures. • In polar solvent system, they self-assembled into nanosheets and granular nanostructures. The self-assembly behavior of perylene diimide (PDI) derivatives has been manipulated to produce nanostructures with exceptional optoelectronic properties. The size and dimension of the aggregates determine their roles in various applications, which are determined by the structure and functionality of the PDI derivatives, including the solvent system in which self-assembly occurred. Herein, we report the synthesis of two new and distinct amphiphilic unsymmetric PDI derivatives. These PDIs contain alkyl chains of varying lengths at one of the imide positions, whereas the other imide position contains a fixed L-alanine substituent. In 90 % hexane or decalin in chloroform, these PDIs were aggregated to form ribbon-like morphologies. In contrast, in a polar solvent system comprised of mixtures of water and acetone, both PDI derivatives self-assembled differently to form distinct morphologies. As the synthesis of PDI-based two-dimensional supramolecular nanosheets has been challenging and also rarely mentioned in the literature, here, we have found that one of the PDI derivatives with long alkyl chain self-assembled to nanosheets in 90 % water/acetone solvent mixture. [Display omitted] [ABSTRACT FROM AUTHOR]

A recent article in the journal Angewandte Chemie International Edition discusses the development of a hydrothermal method for synthesizing naphthalene diimide anolytes for neutral flow batteries. This method improves the solubility and stability of the anolytes, leading to higher capacity and power density. The authors, Gang He et al., suggest that this cost-effective approach could contribute to the commercialization of advanced energy storage technologies by providing a competitive advantage over traditional methods. The article is authored by Xu Liu, Heng Zhang, Chenjing Liu, Zengrong Wang, Xuri Zhang, Haiyan Yu, Yujie Zhao, Ming-Jia Li, Yinshi Li, Ya-Ling He, and Gang He. [Extracted from the article]

Organic-inorganic composites integrating three bay-substituted PDIs with TiO 2 were synthesized, exhibiting enhanced photocatalytic degradation of various organic pollutants and the ability to function without sacrificial agents. [Display omitted] • Three bay-substituted PDIs investigated as organic–inorganic composite photocatalysts. • PDIs' π − π orbital overlap degrees vary from high to low in the aggregates. • PDIBr/TiO 2 effectively photodegrades various organic contaminants. • PDIBr/TiO 2 break down bisphenol A via Z-scheme heterojunction mechanism. This work addresses the challenges associated with the utilization of organic semiconductors, particularly perylene diimide derivatives (PDIs), in photocatalysis. Bay-substituted PDIs have seldom been explored as photocatalysts. In this paper, we synthesized three PDIs with bromine- (PDIBr), fluoroalkyl- (PDIRF), and nitro- (PDING) substituted groups at the bay position. These PDIs were self-assembled through a solvent exchange method on the surface of anatase-phase TiO 2 (A10) to form novel composite materials. The resulting composites showed effective photocatalytic degradation capabilities for various organic contaminants. Notably, the PDIBr/A10 composite achieved 71.04 % degradation efficiency for bisphenol A (BPA) without sacrificial agents and 71.66 % for carbamazepine (CBZ) with a persulfate sacrificial agent within one hour. The PDIBr promoted the π − π orbital overlap in H aggregation, leading to an interfacial layer on TiO 2 that is conducive to charge transfer and reduced recombination, thus enhancing catalytic performance. Furthermore, the Z-scheme heterojunction mechanism was corroborated as the photocatalytic degradation pathway for BPA using the PDIBr/A10 composite as a model. This study provides guiding principles for designing bay-substituted PDI-based composite photocatalysts, presenting new perspectives for the development of efficient photocatalytic systems. [ABSTRACT FROM AUTHOR]

Three polymers with general structure (D-A) n were designed and synthetized to investigate the interaction of strong donors and strong acceptors in polymer chain. They are based on different fused thiophenes (1Th : 4,4′-bis(2-ethylhexyl)-cyclopenta [2,1-b:3,4-b']dithiophene; 2Th : 4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b']dithiophene; 3Th : 4,8-bis(4-fluoro-5-(2-ethylhexyl)-thiophen-2-yl)benzo [1,2-b:4,5-b']bisthiophene) and N , N ′-bis(2-ethylhexyl)-1,8:4,5-naphthalenetetracarboxdiimide (NDI). Fused benzo- and cyclopenta-thiophene derivatives were selected because they are known for their strong electron-donating properties. NDI was coupled with them in polymer chain because it is one of the best known electron withdrawing units. Such combination of donor and acceptor units is one of the strategies for obtaining low band gap conjugated polymers with semiconducting properties for many applications. The interaction of donors and acceptors is a key factor determining the properties of such polymers. The electrochemical and spectroscopic measurement were supported by DFT calculations. Moreover, organic field effect transistors (OFET) were fabricated to demonstrate the feasibility of using the newly developed materials in electronic devices. [Display omitted] • Donor-acceptor polymers based on fused thiophene were characterized. • The results indicate complex relationships between structure and physicochemical properties. • Various properties of polymers influence the performance of OFETs. • Polydispersity and its multimodality are important factors influencing its electronic properties in solid state. [ABSTRACT FROM AUTHOR]

The vinylene-bridged helical perylene diimide dimer (PDI2) and its derivatives have received considerable attention for application in nonfullerene organic solar cells (OSCs). Benefitting from the large natural dipole moment and the reinforced intermolecular forces, a series of asymmetrical non-fullerene acceptors (NFAs) including perylene diimide (PDI) derivatives show comparable and even-better photovoltaic performances in comparison to the symmetrical counterparts. Nevertheless, most of the asymmetrical PDI acceptors were achieved by incorporating a different functional group at the bay position. Breaking the molecular symmetry of PDI at the N position in the imide group is rarely reported. In this contribution, an asymmetrical PDI2 derivative, namely MBI-PDI2, which was constructed by the installation of a mono-benzimidazole group at one of the four imide groups, was synthesized. Using commercially purchased PM6 as an electron donor, a best power conversion efficiency (PCE) of 7.13% was achieved for the MBI-PDI2-based OSCs, which is higher than that of the parent PDI2-based ones. This result demonstrates that structural symmetry-breaking at the N position is a versatile design strategy for high-performance PDI-based NFAs. [ABSTRACT FROM AUTHOR]

The possibility of harnessing the photoactivity of isocyanides in the development of metal-free Ugi-like visible light photo-triggered multicomponent transformations has been reported herein. More in detail, Ugi-3CR, Ugi-Tetrazole-3CR, and Ugi–Joullié-3CR afforded imide peptidomimetic derivatives in good yields and with a wide substrate scope, involving the late-stage editing of complex bioactive scaffolds. Furthermore, a 2-step-one-pot sequence affording linear secondary imides, and a 3-step-one-pot protocol leading to densely functionalized bis-amide derivatives have also been developed to highlight the huge potential of these mild metal-free reaction conditions to afford complex and diverse compounds while being in accordance with the green chemistry principles. [ABSTRACT FROM AUTHOR]

Pure organic room temperature phosphorescence (RTP) materials become increasingly important in advanced optoelectronic and bioelectronic applications. Current phosphors based on small aromatic molecules show emission characteristics generally limited to short wavelengths. It remains an enormous challenge to achieve red and near-infrared (NIR) RTP, particularly for those from nonaromatics. Here we demonstrate that succinimide derived cyclic imides can emit RTP in the red (665, 690 nm) and NIR (745 nm) spectral range with high efficiencies of up to 9.2%. Despite their rather limited molecular conjugations, their unique emission stems from the presence of the imide unit and heavy atoms, effective molecular clustering, and the electron delocalization of halogens. We further demonstrate that the presence of heavy atoms like halogen or chalcogen atoms in these systems is important to facilitate intersystem crossing as well as to extend through-space conjugation and to enable rigidified conformations. This universal strategy paves the way to the design of nonconventional luminophores with long wavelength emission and for emerging applications. Pure organic room temperature phosphorescence (RTP) materials become increasingly important but achieving red and near-infrared (NIR) RTP remains challenging. Here, the authors demonstrate that succinimide derived cyclic imides can emit RTP in the red and NIR spectral range with outstanding efficiencies of up to 9.2%. [ABSTRACT FROM AUTHOR]

Perylene diimides (PDIs), a well‐studied class of organic dyes, have a strong tendency to self‐aggregate in water, thus greatly restricting their phototheranostic applications. Herein, we report a water‐soluble PDI cyclophane "Gemini Box" (GBox‐14+), consisting of a central PDI chromophore enclosed by double‐sided cationic molecular straps. Owing to the effective spatial isolation, the chromophore self‐aggregation can be completely eliminated, even in a concentrated aqueous solution up to 2 mM. To our knowledge, GBox‐14+ represents an interesting example of a fluorescent PDI cyclophane in water, capable of being employed for lysosome‐targetable live‐cell imaging. More importantly, the highly concentrated aqueous solution of PDI radical anion can be significantly stabilized by GBox‐14+ to exhibit an excellent near‐infrared photothermal effect, which was further exploited for efficient and selective antibacterial applications. This work provides a new access to water‐soluble non‐aggregated organic dyes and promotes their potential biomedical applications. [ABSTRACT FROM AUTHOR]

Transition‐metal‐catalyzed regio‐ and stereo‐controllable C−H functionalization remains a formidable challenge in asymmetric catalysis. Herein, we disclose the first example of iridium‐catalyzed C(sp3)−H borylation of aminocyclopropanes by using simple imides as weakly coordinating directing groups under mild reaction conditions. The reaction proceeded via a six‐membered iridacycle, affording a vast range of chiral aminocyclopropyl boronates. The current method features a broad spectrum of functional groups (36 examples) and high enantioselectivities (up to 99 %). We also demonstrated the synthetic utility by a preparative scale C−H borylation, C−B bond transformations, and conversion of the directing group. [ABSTRACT FROM AUTHOR]

A perylene five-membered ring diimide, PDI39, was developed as a new electron-deficient building block for n-type semiconductors. The π-expanded conjugated molecules containing azulenes were synthesized from PDI39. These conjugated molecules show helical geometry and near-infrared absorption up to 810 nm. [ABSTRACT FROM AUTHOR]

A novel SnO2 QDs (quantum dots)/PDI heterojunction photocatalyst was successfully constructed by a simple in‐situ compounded method and exhibited highly enhanced photocatalytic performance and long‐term stability under visible light irradiation. The results of ISI‐XPS and AFM‐KPFM revealed that the effective photo‐generated electrons transferred from PDI supramolecular nanorods to closely attached to SnO2 QDs, which was driven by a giant built‐in electric field across this hetero‐interface, thus highly improved the migration and separation of photo‐generated carriers. Importantly, we have proved for the first time that the formation of heterojunction can effectively hinder the generation of PDI anion radicals (PDI.−), thereby realized improved photocatalytic stability of PDI supramolecular aggregates by reducing the dissociation of PDI supramolecular caused by electrostatic repulsion interaction between PDI.− units. Furthermore, the established high structure and morphology stability also supported its excellent photocatalytic stability. [ABSTRACT FROM AUTHOR]

Due to their strong hydrophobicity and the aggregation-caused quenching effect, the application of perylene diimide (PDI) dyes in biological and medicinal fields lags far behind that of other dyes. Based on a multifunctional encapsulation strategy, we prepared isopropylphenyl sulfone encapsulated PDI dyes (SFPDIs). The four hydrophilic sulfone groups on the bay position of the PDIs not only effectively inhibit the fluorescence quenching caused by π-aggregation but also endow the SFPDIs with good live-cell permeability. The six lipophilic isopropylphenyl groups encapsulate PDI emitters and confer SFPDIs with excellent lipid droplet-targeting ability. Furthermore, the strong electron-withdrawing sulfone groups give the PDIs excellent anti-oxidation ability. [ABSTRACT FROM AUTHOR]

Intrinsic charge transport in molecularly thin organic semiconducting crystals is critically sensitive to the quality of the interfaces required to perform the electrical measurements. Most prominent are the dielectric–semiconductor and semiconductor–metal interface. While impacts from the latter on charge transport can be extracted by four‐terminal measurements, the impact of the dielectric interface can only be minimized, typically by utilizing inert dielectrics. Here, it is shown that charge transport in organic field‐effect transistors based on the n‐type small molecule N, N′‐di((S)‐1‐methylpentyl)‐1,7(6)‐dicyano‐perylene‐3,4:9,10‐bis(dicarboximide) (PDI1MPCN2) can be improved up to one order of magnitude by using hexagonal boron nitride (h‐BN) as dielectric, compared to a standard SiO2 substrate. Using temperature‐dependent electrical measurements, the charge‐transport properties of devices are systematically analyzed, and high four‐terminal mobilities of up to 5.0 cm2 V−1 s−1 are obtained. The high mobility likely stems from decreased charge‐carrier trapping at the semiconductor‐dielectric interface due to the smooth surface of the inert h‐BN. Nevertheless, the temperature dependencies of the mobility, threshold voltage, and interface‐state trap density suggest that charge‐carrier trapping at the dielectric‐semiconductor interface still exists. By comparing the data to transport studies performed on thin air‐gapped organic films, it is concluded that an interfacial layer (likely water or solvent residues) between h‐BN and the monolayer PDI1MPCN2 causes charge trapping. [ABSTRACT FROM AUTHOR]

The complex [Cd(PDNDI)]·DMF (Cd‐PDNDI) (H2PDNDI = N‐(4‐pyridine)‐4,5‐dicarboxy‐1,8‐naphthalene dicarboxyimide) was synthesized by the reaction of N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalene diimide (DPNDI) and Cd(NO3)2·4H2O. It was characterized by elemental analysis, infrared spectroscopy, ultraviolet–visible (UV‐vis) spectroscopy, powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction, and thermogravimetric analysis. Structural analysis shows that the Cd‐PDNDI has a self‐assembled 3D network structure with the rtl type topology. It is worth mentioning that the composition of the ligand is different from the initial raw material used in this molecular structure. This may be because the ligand undergoes an in situ hydrolysis reaction in the reaction system and becomes an NDI carboxylic acid derivative, which continues to join coordination reaction with the metal ion. In addition, the Cd‐PDNDI has an excellent photocatalytic effect on malachite green (MG) among the six dyes, which shows that the Cd‐PDNDI could be used as a photocatalytic material for the degradation of dyes. Highlights: A 3D complex Cd‐PDNDI was synthesized.The Cd‐PDNDI show higher degradation efficiency for MG and can be used as a potential photocatalyst.The possible mechanism of in‐situ reaction of ligands in Cd‐PDNDI is proposed, which provides a reference for the further development of NDI series complexes. [ABSTRACT FROM AUTHOR]

BACKGROUND We aim to determine whether the rationale of designing a tetrameric non‐fullerene acceptor (NFA) to minimize its aggregation compared to its dimer counterparts proves to be a valid strategy in the context of organic photovoltaic (OPV) processing involving solvent additives. We investigate the impact of the molecular design and the processing additive on the thin film formation behavior of four N‐annulated perylene diimide (NPDIx) derivatives. We compare three dimers and a tetramer, processed from a solution containing 1,8‐diiodooctane (DIO), which are used as NFAs and as a processing solvent additive, respectively, in the OPV fabrication. RESULTS: We prepared OPV devices using the PTB7‐Th:NPDIx model system and rationalized the change in their power conversion efficiency (PCE) based on the thin film morphology of the four NDPIx compounds. While the PCE of the OPV devices prepared using the dimers and 1% (v/v) DIO showed a 20–30% drop, those prepared using the tetramer and the same processing conditions showed an 80% drop. Our analysis demonstrates that DIO processing solvent additive‐induced crystallization of the tetramer is the cause of its low performance in OPV devices. CONCLUSION: Our results highlight that relying solely on the tetramer perylene diimide design strategy to prevent the aggregation observed in dimers is not always reliable when processing solvent additives are used in the OPV fabrication. Both the molecular design and the processing solvent additive impact the aggregation behavior of the NFA and need to be taken into account to optimize OPV devices active layer morphology. © 2021 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Chiral organic phosphors with circularly polarized room‐temperature phosphorescence (CPP) provide new prospects to the realm of circularly polarized luminescence (CPL) materials, owing to the long‐lived triplet states and persistent emission. Although several molecular designs show efficient room‐temperature phosphorescence (RTP), realization of ambient organic CPP remains a formidable challenge. Herein, we introduce a chiral bischromophoric phosphor design to realize ambient CPP emission by appending molecular phosphors to a chiral diaminocyclohexane core. Thus, solution‐processable polymer films of the trans‐1,2‐diaminocyclohexane (DAC) chiral cores with heavy‐atom substituted pyromellitic diimide phosphors, exhibits one of the most efficient exclusive CPP emissions with high phosphorescence quantum yield (≈18 % in air and ≈46 % under vacuum) and significant luminescence dissymmetry factor (|glum|≈4.0×10−3). [ABSTRACT FROM AUTHOR]

Imides are an important class of compounds found in the structure of many biologically active and natural compounds. Imides are also important starting materials used in the synthesis of many heterocyclic compounds. Therefore, the synthesis of these compounds has attracted considerable attention and several innovative methods have been developed. Herein, the synthesis of acyclic imides has been reported from nitriles and carboxylic anhydrides in the presence of catalytic amounts of ptoluenesulfonic acid (PTSA) or H2SO4 under microwave irradiation. The reaction has proceeded in better yields with PTSA. When sulfuric acid was used, the product was obtained in lower yields since the degradation was increased. This new microwave-assisted method is compared with conventional heating, and the other methods, reported in the literature. The main advantages of this procedure are shorter reaction times, easier work-up, and good yields. [ABSTRACT FROM AUTHOR]

To prepare soluble polyimides with high temperature resistance, two new diamine monomers, namely, 2,2′-(4,4′-oxybisphenylene)-bis(1-phenyl-5-aminobenzimidazole) (5a), and 2,2′-(4,4′-hexafluoroisopropylidene)-bis(1-phenyl-5- aminobenzimidazole) (5b), were synthesized and exploited to prepare three series of poly(benzimidazole imides)s (PBIIs) by a conventional two-stage synthesis. The resulting PI films were flexible and tough, possessing high glass-transition temperatures (Tgs = 311°C–390°C), improved optical transparency, and excellent solubility. Moreover, the effect of different configuration on performance was revealed, and these data provided a feasible method to enhance both Tg and solubility of PIs by incorporating N-phenyl benzimidazole and corresponding functional moieties. [ABSTRACT FROM AUTHOR]

A novel HPLC method for simultaneous detecting bulky imides and their hydrolyzed products by D-hydantoinase was established. Phthalimide (PI) and 2,3-pyridinedicarboximide (PDI) can be regiospecifically hydrolyzed by engineered strain pET3a-hyd/Escherichia coli BL21(DE3) expressed D-hydantoinase into phthalamic acid (PA) and 3-carbamoyl-α-picolinic acid (α-3CP). The processes were analyzed by HPLC with H2O-acetonitrile as mobile phase containing 0.1% (v/v) trifluoroacetic acid at 254 nm (PDI, α‑3CP and β-2CP) and 220 nm (PI and PA) detector wavelength, respectively. The specific activities of the engineered strain account for 0.15 U/(mL × 10 OD600) to PI and 0.61 U/(mL × 10 OD600) to PDI. [ABSTRACT FROM AUTHOR]

In the field of our research interest, we designed new sulfa drugs–substituted norbornyl imides as prospective bioactive scaffolds by the reaction of endo‐endic anhydride with sulfa drugs followed by reductive Heck reactions of these products. Norbornenyl imides, as starting compounds, and their Heck products were achieved in good yields. Molecular characterization and stereochemistry of the compounds were investigated using Fourier transform infrared, liquid chromatography time‐of‐flight mass spectrometry, proton nuclear magnetic resonance, carbon 13 attached proton test, H‐H correlation spevtroscopy, and nuclear overhauser enhancement spectroscopy experiments. The Heck products of norbornenyl imides showed exo‐selectivity. All eight novel synthesized compounds, including two sulfa drugs–based norbornenyl imides and six exo‐5‐aryl‐ substituted norbornyl imides, as well as standard sulfonamides, were evaluated for antimicrobial activity against nine microorganisms consisting of Gram‐negative bacteria, Gram‐positive nonactinobacteria, actinobacteria, and yeast. The most active compound was 3a against actinobacteria. The efficacy of 2 and its derivatives against the studied strains were weaker than 3 and its derivatives, but all the studied samples exhibited antifungal potency. [ABSTRACT FROM AUTHOR]

The two‐electron reduced forms of perylene diimides (PDIs) are luminescent closed‐shell species whose photochemical properties seem underexplored. Our proof‐of‐concept study demonstrates that straightforward (single) excitation of PDI dianions with green photons provides an excited state that is similarly or more reducing than the much shorter‐lived excited states of PDI radical monoanions, which are typically accessible after biphotonic excitation with blue photons. Thermodynamically demanding photocatalytic reductive dehalogenations and reductive C−O bond cleavage reactions of lignin model compounds have been performed using sodium dithionite acts as a reductant, either in aqueous solution or in biphasic water–acetonitrile mixtures in the presence of a phase transfer reagent. Our work illustrates the concept of multi‐electron reduction of a photocatalyst by a sacrificial reagent prior to irradiation with low‐energy photons as a means of generating very reactive excited states. [ABSTRACT FROM AUTHOR]

We present the synthesis and catalytic properties of two novel telluroniobates {Te15Nb21} and {Te10Nb14}. {Te15Nb21} is the first trimeric telluroniobate with the largest number of tellurium atoms in the Te–Nb system. Besides, both clusters exhibit excellent catalytic activity in the amidation reactions of anhydrides and amines, and cyclic imides and bi-amides can be controllably synthesized, which represents a breakthrough in the catalysis of polyoxoniobates. [ABSTRACT FROM AUTHOR]

Efficient organic photovoltaics (OPV) based on SnO2 | perylene diimide (PDI) bilayer as an electron transport layer (ETL) is fabricated and tested in an ambient environment. The PTQ10:Y6 photoactive system is used as the primary bulk‐heterojunction. Without any surface treatment, the power conversion efficiency (PCE) of SnO2‐based OPV devices is 1.5%. Treating the SnO2 nano‐particles with UV‐ozone and then applying a layer of N‐annulated PDI with a functional NH bond (PDIN‐H) on top increase device PCEs to 9.2%. For indoor applications, the OPV device PCE rises from 8.1% to 12.3% when PDIN‐H is employed on SnO2 and tested under low light conditions, without the need for light soaking. The SnO2 | PDIN‐H ETL bilayer is slot‐die coated and corresponding OPV devices have a PCE of 7.9%, demonstrating utility for OPV scale‐up. The hybrid ETL is tested with other photoactive systems employing Y6, Y7, and IDIC as acceptors, as well as PM6 donor, and all these cases yield OPV devices with improved PCE when compared to OPV devices with SnO2‐only ETLs. These results show the successful implementation of SnO2 | PDIN‐H as an ETL for OPV. [ABSTRACT FROM AUTHOR]

Inspired by the advantages of heteroatoms introducing and molecular structure symmetry‐breaking in construction of non‐fullerene acceptors (NFAs), in this contribution, we designed and synthesized three asymmetric perylene diimide (PDI) based acceptors by annulating a selenophene and/or fusing a thiophene ring at the bay position. Using commercially purchased PBDB−T as electron donor, a best power conversion efficiency (PCE) of 5.32 % was achieved for selenophene‐annulated PDI (PDI2−Se), while higher PCE of 6.10 % was obtained for the thiophene fused one (PDI2−FT). Interestingly, PDI2Se−FT, in which the S and Se atoms introduced simultaneously, showed the best photovoltaic performance among the three asymmetric NFAs with an optimal PCE of 6.96 %. This result demonstrates that incorporation of diverse heteroatoms at the bay positions to construct asymmetric configuration is a robust design strategy for high performance PDI‐based NFAs. [ABSTRACT FROM AUTHOR]

Tf2NH-assisted BINAM-derived thiophosphoramide catalysis has been accomplished for the enantioselective oxysulfenylation of o-vinylanilides with N-(aryl/alkylthio)imides. The developed reaction offers access to diverse substituted aryl/alkylthio tethered 3,1-benzoxazines in excellent yields and enantiomeric ratios. Furthermore, synthetic applications of benzoxazines and aryl/alkylthio moieties and a transition state model for the observed enantioselectivity are also discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • PDI/CuS supramolecular heterojunction was synthesized by two-step self-assembly strategy. • PDI/CuS showed enhanced photoactivity and photostability. • Highly ordered H-type π-π stacking and p-n heterojunction could accelerate the separation of the photo-generated h+-e− pairs. • Photocatalytic mechanism and the possible degradation process of TC was studied in detail. Developing photocatalysts that are inexpensive and efficient in degrading pollutants are essential for environmental remediation. Herein, a novel system of perylene diimide (PDI)/CuS p-n heterojunction was synthesized by a two-step self-assembly strategy for removal of tetracycline in waste water. Results showed that PDI/CuS-10% exhibited highest photocatalytic behavior. The apparent rate constants for tetracycline (TC) degradation for the blend were 5.27 and 2.68 times higher than that of CuS or PDI, respectively. The enhancement of photocatalytic activity was mainly attributed to the π–π stacking and p-n junction, which can accelerate the separation of the photo-generated h+-e− pairs. Besides, the light absorption of PDI/CuS from 800 to 200 nm was significantly enhanced and the absorption edge even reached the near-infrared region, which also played an important role in providing desired photocatalytic properties. Surprisingly, PDI/CuS could maintain high catalytic activity even after 5 cycles under simulated conditions, indicating that the composite had high potential for practical applications. Owing to high efficiency, low cost and wide application range, the PDI/CuS nanocomposites are promising candidates for environmental remediation. [ABSTRACT FROM AUTHOR]

New N-silylated phthalimides, succinimides, and 1,8-napthalimides were synthesised by reactions of the alkali imides with chlorosilanes in THF. Six different mono-, di-, tri- and tetra-iminosilanes of the type (CH3)4–nSi(imide)n were obtained and the products analysed with 1H, 13C, 29Si NMR, and Raman spectroscopy. The molecular structures of four imidosilanes have been determined by single-crystal X-ray diffraction. A characteristic structural feature of the compounds is the fact that all intramolecular Si⋯O distances are significantly below the sum of the van-der-Waals radii of silicon and oxygen of 3.62 Å. Experimentally found values for Si⋯O distances range from 2.813 to 3.030 Å. However, there are no significant orbital interactions between silicon and oxygen atoms, as shown by quantum chemical analysis with AIM and NBO methods. The short Si⋯O distances in these molecules are caused by the geometry of the rigid imide group bound to the silicon atom, and there is no evidence for an increase of the coordination number of the Si atoms. [ABSTRACT FROM AUTHOR]

A perylene diimide (PDI) derivative was used as the third component to prepare high‐efficiency ternary organic solar cells (OSCs). PDI derivatives usually bear a wide bandgap and a long exciton diffusion length, which could be helpful to promote the device efficiency and still retain a high open‐circuit voltage (Voc). Compared with the binary OSC, the photovoltaic performance improved. Further changing the method for preparing the processing solutions from dissolving the polymer donor and small‐molecule acceptor ITTC together to dissolving them individually, molecular packing in the deposited active layer could be adjusted and the short‐circuit current density could be increased. As a result, the final device efficiency in such OSCs achieved 12.29 % power conversion efficiency (PCE) with a high Voc of 0.93 V. When using the PDI derivative as the third component to D18 : BTP‐eC9‐based OSCs, a high PCE of 17.38 % was obtained, which is the best one among photovoltaic devices employing PDI derivatives. [ABSTRACT FROM AUTHOR]

Herein, a series of supramolecular self-assembled perylene diimide (PDI) nanomaterials by different solvents have been successfully prepared. Under visible-light irradiation, the self-assembled PDI supramolecular material pretreated by acetone (PDI (acetone)) exhibited superior photocatalytic degradation activity on bisphenol A (BPA) and Rhodamine B (RhB), which were 7.1 times and 4.2 times that of the monomeric PDI, respectively. The improved photo-degradation activity was mainly attributed to the rapid separation and transfer of the photogenerated carriers and π–π interaction between self-assembled PDI supramolecules. The analysis of free radical trapping experiments and ESR characterization together indicated that h+ and ˙O2− are the main active species to rapidly degrade pollutants. Meanwhile, this work also studied the influence of other solvents (e.g., deionized water, methanol, and ethanol) on the self-assembly process of monomeric PDI. In summary, this study provides a new strategy to develop highly efficient self-assembled PDI photocatalysts by different solvents. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of six new N-annulated perylene diimide (N-PDI) molecules consisting of different alkyl-based heteroatom and waxy infused sidechains is reported. Amino, urea, quaternary methyl ammonium, iminopyridine, hexadecyl and pyridine moieties were all appended to the pyrrolic N-position of N-annulated PDI. These N-PDI derivatives have been synthesized using facile SN2 chemistry resulting in high yields and without the need for purification via column chromatography. To further demonstrate the functional diversification offered by N-PDI we appended a cyano group to the 6,7-bay positions opposite the N-annulation site and tested utility in organic field effect transistor devices. Complete characterization of these N-PDI derivatives was completed using UV-Vis spectroscopy, cyclic voltammetry and solubility determination to observe how the appended sidechains affect structure–properties relationships. [ABSTRACT FROM AUTHOR]

A green and practical divergent Ritter-type amination via a photoredox catalytic four-component radical-polar crossover process was developed. This versatile protocol presents a modular and powerful strategy to access functionalized β-sulfonyl imides and imines under mild conditions from readily available and stable substrates with high atom-, step- and redox economy. We manipulated carboxylic acids and benzotriazoles to precisely attack the nitrilium ion instead of the carbocation, thus preventing many complicated side reactions of the photocatalytic reactions. Furthermore, the synthetic utility of this divergent Ritter reaction is further demonstrated by the late-stage modification of pharmaceutical and natural product derivatives. [ABSTRACT FROM AUTHOR]

We have synthesized and characterized putrescine based 2G dendron bearing oligocarboxylic acid as hydrophilic groups (protected as tert‐butyl group) at peripheral positions. The multi‐step synthesis of 2G dendron has been carried out through orthogonal protection‐deprotection strategy. This putrescine based 2G dendron is further utilized for N‐Imide functionalization of perylene dianhydride through imidization reaction to obtained tert‐butyl‐protected PDI 2 followed by acidic deprotection to furnish highly water‐soluble bola‐amphiphile PDI 1. The newly synthesized compounds were characterized by NMR‐spectroscopy, Mass spectrometry, IR as well as by elemental analysis. The PDI 1 showed increased water solubility in acidic and basic mediums. [ABSTRACT FROM AUTHOR]