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Thio-benzothioxanthene imide (BTXI) exhibits long excited state lifetime (τT = 17.7 μs) and high ISC efficiency (ΦΔ = 97%). For the first time, BTXI derivatives were used as photosensitizers for triplet–triplet annihilation upconversion, achieving the highest efficiency of 13.8%. In addition, thio-BTXI derivatives were used as photoinitiators for photopolymerization, resulting in a series of green light-activated radical polymerization systems. [ABSTRACT FROM AUTHOR]

In this study, we efficiently sensitize pyromellitic diimide's triplets by cocrystallizing with heavy bromine-substituted small aromatics. The resulting halogen bonding interactions mediate an external heavy atom effect, leading to remarkable ambient phosphorescence with one of the highest quantum yields reported to date. [ABSTRACT FROM AUTHOR]

Some syndiotactic-rich polyolefins, generally difficult to synthesize through stereospecific polymerization of the corresponding monomers, were prepared by homogeneous non-catalytic hydrogenation of syndiotactic 1,2 poly(1,3-diene)s with diimide, arising from thermal decomposition of p-toluene-sulfonyl-hydrazide. All the polymers synthesized were structurally characterized by means of several analytical techniques, such as FT-IR, NMR (1H, 13C and 2D), DSC, and GPC, and herein illustrated. [ABSTRACT FROM AUTHOR]

The pursuit of innovative organic materials and the examination of the “structure‐function” correlation in lithium‐ion batteries (LIBs) are crucial and highly desirable. Current research focuses on the creation of novel conjugated organic polymers with polycarbonyl groups and examining the impact of electrode structure on the function of lithium‐ion batteries. In this paper, two novel cyanovinylene‐based conjugated organic polymers, NBA‐TFB and NBA‐TFPB, are synthesized using a Knoevenagel condensation reaction with naphthalene diimide as the integral unit. The performance of NBA‐TFB and NBA‐TFPB as cathodes in lithium‐ion batteries is investigated. Improved conductivity and increased active site density in NBA‐TFPB resulted in superior electrochemistry compared to NBA‐TFB. Specifically, NBA‐TFPB exhibited a larger reversible capacity (87.58 mAh g−1 at 0.2C and 88.34% retention after 100 cycles), exceptional rate capability (66.13 mAh g−1 at 5C), and robust cycling stability (99.58% coulombic efficiency at 1C and 60.71% retention after 2000 cycles). This study expands the family of diimide‐based naphthalene polymers and provides a strategy for enhancing the performance of organic electrode materials containing polycarbonyl structure. [ABSTRACT FROM AUTHOR]

The synthesis of charge assisted amidinium...phosphonate hydrogen-bonded organic frameworks (HOFs) is reported. Two tectons, with either a biphenyl or naphthalene diimide backbone, were combined with bis-amidinium salts to afford HOF1 and HOF2, respectively. Whereas HOF1 formed rapidly, typically within two days of mixing, HOF2 proved more challenging to synthesise. Interestingly, the presence of sunlight facilitated the rapid formation of HOF2 within a few hours. Although crystals of tectons 1H4 or 2Et4 exhibited densely packed structures, combination of the corresponding phosphonate bases with bisamidinium cations, through amidinium...phosphonate interactions, gave open framework materials. The HOFs formed through this approach exhibited notable stability limitations, including a propensity for phase transformations or structural collapse upon solvent removal. [ABSTRACT FROM AUTHOR]

We report a liquid material based on an L -valine-appended pyromellitic diimide framework. This liquid adopts a room-temperature liquid with Tg at −50 °C and can dissolve naphthalene derivatives to show various photoluminescent colors. Furthermore, the on/off photoluminescence of these solutions can be controlled by heating. [ABSTRACT FROM AUTHOR]

The cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor‐acceptor (D–A) typed selenophene‐fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non‐fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self‐doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8‐BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3‐based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8‐BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high‐efficiency CIMs for OSCs. [ABSTRACT FROM AUTHOR]

We report an electrochemically promoted decarboxylation of readily available carboxylic acid and subsequent Mumm rearrangement to synthesize the corresponding imides. The reaction features external oxidant‐free, transition metal‐free mild conditions, and good functional group tolerance, affording various imides in moderate to good yields. Mechanistic studies reveal that the selective oxidation of aliphatic carboxylic acids appears to be the key step in this transformation. [ABSTRACT FROM AUTHOR]

Multipurpose applications of a newly developed homobimetallic Ru(II) complex, Ru‐NDI[PF6]4, which incorporates 1,10‐phenanthroline and triazole‐pyridine ligands and linked via a (−CH2−)3 spacer to the reputed anion‐π interacting NDI system, are described. Solution‐state studies of the bimetallic complex, including EPR, PL, UV‐vis, and NMR experiments, reveal two sequential one‐electron transfers to the NDI unit, generating NDI⋅− and NDI2− in the presence of F− selectively. This process inhibits the primary electron transfer from Ru(II) to the NDI unit, thereby allowing the 3MLCT‐based emission of the complex to be recovered, resulting in a corresponding ten‐fold increase in luminescence intensity. DFT and TD‐DFT computational studies further elucidate the experimentally observed absorption spectra of the complex. Secondly, CT‐DNA binding studies with the complex are performed using various spectroscopic analyses such as UV‐vis, PL, and CD. Comparative DNA binding studies employing EB and molecular docking reveal that the binding with CT‐DNA occurs through both intercalative and groove binding modalities. Thirdly, the photocatalytic activities of the complex towards C−C, C−N, and C−O bond formation in organic cross‐coupling reactions, including the amidation of α‐keto acids to amines and the oxidation of alcohol to aldehydes, are also demonstrated. [ABSTRACT FROM AUTHOR]

The development of concise and efficient methods to construct bithiophene derivatives is an appealing task in the fields of organic chemistry and organic functional materials. Herein, we summarize our recent efforts towards the development of catalytic oxidative C–H cyclization reactions of thiophenol derivatives with 1,3-diynes, which provides a straightforward and effective synthetic approach to both symmetrical and nonsymmetrical 3,3′-bibenzothiophenes. This work is expected to stimulate the application of catalytic oxidative C–H annulation of aromatics with 1,3-diynes for the exploitation of organic functional materials. [ABSTRACT FROM AUTHOR]

We report the synthesis, structures and gas sorption studies of two three-dimensional (3D) metal–organic frameworks (MOFs) namely {[Zn2(OBZ)2L1]·4DMF}n (1) and {[Co3(TER)3(L2)(DMF)]·5DMF}n (2), where OBZ2− is deprotonated 4,4′-oxybis(benzoic acid), TER2− is deprotonated terephthalic acid, DMF is N,N-dimethylformamide, L1 is 2,2′-bis(pyridin-3-ylmethyl)-[5,5′-biisoindoline]-1,1′,3,3′-tetraone and L2 is 5,5′-carbonylbis(2-(pyridin-3-ylmethyl)isoindoline-1,3-dione). 1 and 2 are 3D MOFs containing 2D channels. The desolvated phases of 1 and 2 (1-d and 2-d) adsorb modest amounts of carbon dioxide (CO2) at 195 K and 273 K; however, 1-d displays stepwise adsorption of CO2 at 195 K and hysteretic desorption. Notably, a gate-opening effect is triggered after 1-d adsorbs 63 cm3 (STP) g−1, allowing the structure to open and adsorb an additional 54 cm3 (STP) g−1. In contrast, 1-d adsorbs relatively small amounts of hydrogen (H2) and nitrogen (N2) gases, 3 cm3 (STP) g−1 and 12 cm3 (STP) g−1, respectively, suggesting selectivity of CO2 over H2 and N2. [ABSTRACT FROM AUTHOR]

We have successfully constructed a PDI supramolecular material, s-PDI- P 1, with an intermolecular double hydrogen bonding structure, which has a compact H-type π-π stacking structure and achieves high carrier separation and migration efficiency. The oxygen evolution rate of the s-PDI- P 1 was 3.23 mmolg-1h−1, without the use of precious metal co-catalysts. [Display omitted] • In the absence of a noble metal co-catalyst, the s-PDI- P 1 molecule exhibited the highest oxygen evolution rate of 3.23 mmolg-1h−1. • The formation of a double hydrogen-bonded structure resulted in a tight H-type π-π stacking between the s-PDI- P 1 molecules, leading to the creation of an ultrathin nanosheet structure with a thickness of 4.7 nm. • s-PDI- P 1 with higher photocurrent intensity (87.2 μA) and lower internal resistance (0.32 KΩ). • s-PDI- P 1 has a higher valence band position (+1.5 V). Perylene diimides (PDI) are widely used in photocatalytic oxygen evolution due to their deep valence band potentials. Here, we report the synthesis of a unique supramolecular photocatalyst (designated s-PDI- P 1) by introducing hydroxyl and carboxyl groups at the imide position of PDI. This modification allows the formation of intermolecular double hydrogen bond structures between the hydroxyl groups, oxygen atoms on the perylene cores and the carboxyl groups. The resulting double hydrogen bonding structures reduce lateral slip and promote the formation of supramolecular structures with H-type π-π stacking. In addition, the intermolecular hydrogen bonding interactions between the hydroxyl groups and the oxygen atoms on the perylene cores bring the PDI molecules closer together, enhancing the conjugation of the PDI supramolecules and facilitating the formation of ultrathin nanosheet-like structures. In this study, we successfully constructed ultrathin nanosheets of the supramolecular photocatalyst s-PDI- P 1 with a compact H-type π-π stacking structure, which exhibited enhanced charge transfer capability, shorter charge migration distance, and achieved a high photocatalytic oxygen evolution rate of 3.23 mmolg-1h−1. These results highlight the potential of intermolecular double hydrogen bond structures to improve the separation and migration driving force of photogenerated charges, thus providing a novel design strategy for organic photocatalysts. [ABSTRACT FROM AUTHOR]

Anthracene carboximides (ACIs) conjugated with gluco‐, galacto‐ and mannopyranosides are synthesized, by glycosylation of N‐hydroxyethylanthracene carboximide acceptor with glycosyl donors. Glycoconjugation of anthracene carboximide increases the aq. solubility by more than 3‐fold. The glycoconjugates display red‐shifted absorption and emission, as compared to anthracene. Large Stokes shift (λabs/λem=445/525 nm) and high fluorescence quantum yields (Φ) of 0.86 and 0.5 occur in THF and water, respectively. The ACI‐glycosides undergo facile photodimerization in aqueous solutions, leading to the formation of the head‐to‐tail dimer, as a mixture of syn and anti‐isomers. Solution phase and solid‐state characterizations by dynamic light scattering (DLS), microscopic imaging by atomic force (AFM) and transmission electron (TEM) microscopies reveal self‐assembled vesicle structures of ACI glycosides. These self‐assembled structures act as multivalent glycoclusters for ligand‐specific lectin binding, as evidenced by the binding of Man‐ACI to Con A, by fluorescence and turbidity assays. The conjugates do not show cellular cytotoxicity (IC50) till concentrations of 50 μM with HeLa and HepG2 cell lines and are cell‐permeable, showing strong fluorescence inside the cells. These properties enable the glycoconjugates to be used in cell imaging. The non‐selective cellular uptake of the glycoconjugates suggests a passive diffusion through the membrane. [ABSTRACT FROM AUTHOR]

The backwardness of n‐type organic semiconductors still exists compared with the p‐type counterparts. Thus, the development of high‐performance n‐type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay‐region‐annulated PDI derivatives, has drawn considerable attentions. However, the electronic mobilities of azabenzannulated PDI derivatives are barely satisfactory. In this contribution, the peripheral benzene ring in azabenzannulated PDI 2 was fused to the ortho position by intramolecular C−H arylation cyclization. This endows the resultant azabenzannulated PDI 4 a planar configuration as well as electron deficient pentagonal ring. As a result, the electronic mobility of 4 is almost two orders of magnitude higher than that of the nonfused azabenzannulated PDI 2. This work shall pave a new avenue in elevating the performance of azabenzannulated PDI in organic electronics. [ABSTRACT FROM AUTHOR]

The combination of photothermal therapy (PTT) and chemotherapy has been extensively investigated as a promising anticancer strategy, which can maximize therapeutic effects, reverse multidrug resistance, and reduce side effects. However, a conventional nanodrug delivery system incorporating a photothermal agent and chemotherapeutic drug together shows some disadvantages, including lower drug loading content, complex preparation process, and unpredictable safety risks of the carrier. Herein, a perylene diimide (PDI) derivative, PDI0, was synthesized as a photothermal agent, which could co-assemble with the chemotherapeutic drug DOX to develop novel multifunctional supramolecular nanodrugs. The prepared nanodrugs DP1, DP2, and DP3 with ultra-high drug loading capacity were carefully characterized by UV-vis absorption spectroscopy, fluorescence spectroscopy, DLS, and TEM. Notably, DP2 showed an appropriate average size of ∼73.4 nm. DP2 was sensitive to the stimuli of external light and internal lysosome acidic pH, and the photothermal conversion efficiency (η) was ∼54.34%. The photothermal and photoacoustic (PA) dual-mode imaging and anticancer effect were further evaluated by in vitro and in vivo investigations. Therefore, our prepared carrier-free nanodrug DP2 may have potential applications for dual-mode imaging guided synergistic PTT-chemotherapy. [ABSTRACT FROM AUTHOR]

A combined computational and experimental approach allowed us to develop overall the most selective catalyst for the direct hydrogenation of N‐methyl, N‐alkyl and N‐aryl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99 % enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H‐bonding of the imide C=O with the substrate iminium ion and a stabilizing π–π interaction with the cyclometallated ligand. The cyclometallated ligand thus exhibits a unique mode of action, serving as a template for the H‐bond directed approach of the substrate which results in enhanced selectivity. The catalyst (2) has been synthesized and isolated as a crystalline air‐stable solid. X‐ray analysis of 2 confirmed the structure of the catalyst and the correct position of the imide C=O groups to engage in an H‐bond with the substrate. 19F NMR real‐time monitoring showed the hydrogenation of N‐methyl imines catalyzed by 2 is very fast, with a TOF of approx. 3500 h−1. [ABSTRACT FROM AUTHOR]

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate the transition of renewable energy sources from auxiliary to primary energy, the commercial production of anolyte materials still suffers from insufficient performance of high‐concentration and the high cost of the preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology and introduces the charged functional groups into hydrophobic naphthalene diimide cores, and prepares a series of high‐performance naphthalene diimide anolytes. Under the synergistic effect of π–π stacking and H‐bonding networks, the naphthalene diimide exhibits excellent structural stability and the highest water solubility (1.85 M for dex‐NDI) reported to date. By employing the hydrothermal method, low‐cost naphthalene diimides are successfully synthesized on a hundred‐gram scale of $0.16 g−1 ($2.43 Ah−1), which is also the lowest price reported to date. The constructed full battery achieves a high electron concentration of 2.4 M, a high capacity of 54.4 Ah L−1, and a power density of 318 mW cm−2 with no significant capacity decay observed during long‐duration cycling. These findings provide crucial support for the commercialization of AORFBs and pave the way for revolutionary developments in neutral AORFBs. [ABSTRACT FROM AUTHOR]

A series of conjugated polymers bearing thiophene‐based donors and pyromellitic diimide (PMDI) acceptor were prepared, and their electrochromic (EC) properties were studied via using fabricated thin‐film EC devices. It was observed that structurally regular alternating polymers with fewer (1 and 2) thiophene donors do not exhibit any EC properties while increasing the number of donors eventually led to the emergence of orange‐red‐to‐green colour switching. On this basis, two more random co‐polymers containing higher donor‐to‐acceptor ratios were synthesized to further improve EC switching properties. The two polymers, which bear a PMDI‐to‐thiophene ratio of ca. 1 : 7 and 1 : 8, revealed orange red‐to‐blue colour switching and generally improved optical contrasts and switching speeds in both the visible and near infra‐red (NIR) region. In addition, the subtle modulation of polymer colour and hue via variation of the number of thiophene donors was evident through colorimetric study. This work therefore demonstrates the potential and possibility of using the PMDI acceptor unit to construct EC‐active conjugated polymers, and considerations for future tuning of colour and switching performances. [ABSTRACT FROM AUTHOR]

n‐Bu4NI/K2S2O8 mediated C−N coupling between aldehydes and amides is reported. A strong electronic effect is observed on the aromatic aldehyde substrates. The transformylation from aldehyde to amide takes place exclusively when an aromatic aldehyde bears electron‐donating groups at either the ortho or para position of the formyl group, while the cross‐dehydrogenative coupling dominates in the absence of these groups. Both the density functional theory (DFT) thermochemistry calculations and experimental data support the proposed single electron transfer mechanism with the formation of an acyl radical intermediate in the cross‐dehydrogenative coupling. The n‐Bu4NI/K2S2O8 mediated oxidative cyclization between 2‐aminobenzamide and aldehydes is also reported, with four quinazolin‐4(3H)‐ones prepared in 65–99 % yields. [ABSTRACT FROM AUTHOR]

Solar‐driven photocatalysis employing particulate semiconductors represents a promising approach for sustainable production of valuable chemical feedstock. Metal poly(heptazine imide) (MPHI), a novel 2D ionic carbon nitride, has been recognized as an emerging photocatalyst with distinctive properties. In this minireview, we first delineate the forefront innovations of MPHI photocatalysts, spanning from synthetic strategies and solving structures to the exploration of novel properties. We place special emphasis on the structural design principles aimed at developing high‐performance MPHI systems toward photocatalytic solar fuel production such as H2 evolution, H2O oxidation, H2O2 production and CO2 reduction. Finally, we discuss crucial insights and challenges in leveraging highly active MPHIs for efficient solar‐to‐chemical energy conversion. [ABSTRACT FROM AUTHOR]

1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) catalyzed Michael addition reactions between α,β‐unsaturated esters and benzophenone‐imines of glycine esters have been realized in THF at room temperature by using LiBr as an additive, effectively enabling the glutamation of phenols, thiophenols, secondary amines and imides. 3‐Substituted glutamic acid esters were obtained in excellent yields and diastereoselectivities (up to quantitative yield and >20 : 1 dr). These glutamic acid esters were readily converted into their corresponding pyroglutamic acid esters in high yields through acidic hydrolysis followed by lactamization. [ABSTRACT FROM AUTHOR]

The [4+2] dimerization of arylmaleic acid imides, which occurs in the presence of 3,5-dimethyl-1H-pyrazole on solid media under convection or microwave heating, has been studied. It was shown that dimerization proceeds stereoselectively with the formation of polycyclic compounds with a decahydrobenzo[e]pyrrolo[3,4-g]isoindole skeleton, predominantly of the endo-configuration. The best results in yields and stereoselectivity were achieved when reactions were carried out on silica gel under microwave activation conditions. [ABSTRACT FROM AUTHOR]

Targeting the challenges of inadequate charge separation and insufficient molecular activation within the photocatalyst, we have successfully developed a novel supramolecular polarization photocatalyst with methylphosphate-substituted PDI (P-PDIP), which features a significant built-in electric field, resulting in substantial enhancements in both charge separation efficiency and molecule activation efficiency, thereby paving the way for an efficient and stable photocatalytic selective aerobic oxidation of sulfides. [Display omitted] • A novel P-PDIP supramolecular polarization photocatalyst is constructed for selective aerobic oxidation of sulfide. • A giant build-in electric field is produced in P-PDIP by molecular dipole modulation and polar molecular self-assembly. • The incorporation of methylphosphate groups improves the activation efficiency of O 2 and thioether molecules. • The P-PDIP achieves 99.9% conversion and 99.8% selectivity in the aerobic oxidation of methyl phenyl sulfide to sulfoxide. Photocatalytic aerobic oxidation is a promising sustainable strategy for the selective organic synthesis of industrially valuable chemicals. However, the poor charge separation and insufficient molecular activation restrict the overall photocatalytic efficiency. To address these issues, we have developed a novel approach involving molecular dipole modulation and polar molecular self-assembly to modulate the built-in electric field (BEF) in perylene diimide (PDI) supramolecular polarization photocatalysts by adjusting the electronegativity of terminal substituents. The optimized methylphosphate-substituted PDI (P-PDIP) supramolecular system features the strongest BEF induced by its large molecular dipole, with an intensity 3.89 times higher than that observed in methylcarboxy-substituted PDI (P-PDIC) and 5.64 times higher than that observed in P-PDI. This significant enhancement in BEF generates a powerful driving force within P-PDIP, facilitating directional charge separation toward active sites. Additionally, the incorporation of methylphosphate groups improves the activation efficiency of O 2 and thioether molecules, resulting in a remarkable photocatalytic performance for selective aerobic oxidation of sulfides into sulfoxide (up to 99.9% conversion and 99.8% selectivity). This study highlights that enhancing BEF through manipulating molecular dipoles can significantly improve photocatalytic activity, offering great potential for constructing efficient organic polarization photocatalysts in green chemistry and sustainable production. [ABSTRACT FROM AUTHOR]

[Display omitted] • The self-standing COFM PDI-THSTZ is synthesized via liquid–liquid interfacial method. • The semiconductor characteristics of PDI and multi-channel structure of COF endow the sensor with real-time sensing properties. • The mechanism for the enhanced TMA sensing response of COFM PDI-THSTZ is investigated. • The TMA sensor can be used for the quality monitoring in IoT. The unprecedented demand for highly selective, real-time monitoring and low-power gas sensors used in food quality control has been driven by the increasing popularity of the Internet of Things (IoT). Herein, the self-standing perylene diimide based covalent organic framework membranes (COFM PDI-THSTZ) were prepared via liquid–liquid interfacial synthesis method. By incorporating the perylene diimide monomer into the COFM through molecular engineering, COFM PDI-THSTZ based sensor demonstrated an outstanding trimethylamine (TMA)-sensing performance at room temperature. Benefited from the TMA-accessible self-standing membrane morphology, π-electron delocalization effect, and extensive surface area with continuous nanochannels, the specific and highly sensitive TMA measurement has been achieved within the range of 0.03–400 ppm, with an exceptional theoretical detection limit as low as 10 ppb. Moreover, the primary internal mechanism of COFM PDI-THSTZ for this efficient TMA detection was investigated through in-situ FT-IR spectra, thereby directly elucidating that the chemisorption interaction of oxygen modulated the depletion layers on sensing material surface, resulting in alterations in sensor resistance upon exposure to the target gas. For practical usage, COFM PDI-THSTZ based sensor exhibited exceptional real-time in-situ sensing capabilities, further confirmed their potential for application in dynamic prediction evaluation of marine fish products and quality monitoring in IoT. [ABSTRACT FROM AUTHOR]

Decatungstate is a potent photocatalyst for hydrogen atom transfer (HAT) but faces degradation issues when using a typical tetra-n-butylammonium salt. Herein, we employed tetraphenylphosphonium as a countercation to yield a highly durable and efficient HAT photocatalyst, enabling α-oxygenation of amides to their corresponding imides using O2 as an oxidant. [ABSTRACT FROM AUTHOR]

It is crucial to prepare high-mobility organic polycrystalline film through solution processing. However, the delocalized carrier transport of polycrystalline films in organic semiconductors has rarely been investigated through Hall-effect measurement. This study presents a strategy for building strong intermolecular interactions to fabricate solution-crystallized p-type perylene diimide (PDI) dianion films with a closer intermolecular π–π stacking distance of 3.25 Å. The highly delocalized carriers enable a competitive Hall mobility of 3 cm2 V−1 s−1, comparable to that of the reported high-mobility organic single crystals. The PDI dianion films exhibit a high electrical conductivity of 17 S cm−1 and typical band-like transport, as evidenced by the negative temperature linear coefficient of mobility proportional to T −3/2. This work demonstrates that, as the intermolecular π–π interactions become strong enough, they will display high mobility and conductivity, providing a new approach to developing high-mobility organic semiconductor materials. [ABSTRACT FROM AUTHOR]

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10−3 cm2 V−1 s−1 and 2.1 × 10−3 cm2 V−1 s−1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure–function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications. [ABSTRACT FROM AUTHOR]

Although the synthesis of vinyl triflates has a long history, the synthesis of vinyl bis(perfluoroalkanesulfonyl)imides has not been reported yet. Here, we report a simple synthetic route to vinyl bis(perfluoroalkanesulfonyl)imides that does not require any additives. The stereoselectivity originates from the steric hindrance between the aryl group and the imide. The reaction proceeds chemoselectively, and subsequent cyclization provides the 1‐amino‐3‐aryl naphthalene derivatives. [ABSTRACT FROM AUTHOR]

The amino acid unit carrying cyclic naphthalene diimide (cNDI) was synthesized by linking the amino moiety of cNDI as a G4‐specific ligand with the γ‐carboxylic acid moiety of Fmoc‐Glu. cNDI‐peptide‐dimer, 1 was synthesized by peptide synthesizer using this unit. 1 exhibited an extremely strong binding constant of the order of 108 M−1 with telomeric G4 dimer, probably due to cooperative stacking of the its two G4 planes. It also showed an IC50 at the nM level by the TRAP assay. The results obtained here are expected to enable the design of peptide ligands with multiple cNDI sites targeting the G4 cluster by using the amino acid units of cNDI. [ABSTRACT FROM AUTHOR]

The development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor‐acceptor type of conjugated macrocycle (CDI‐CPP) featuring intramolecular charge‐transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X‐ray crystallography. Transient spectroscopy studies showed that CDI‐CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5 ns and 238 ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra‐ and intermolecular charge‐transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions. [ABSTRACT FROM AUTHOR]

A variety of enantioenriched substituted imides were facilely synthesized through aerobic oxidation/allylic amination reactions of aldimines with MBH carbonates under N-heterocyclic carbene (NHC)/chiral tertiary amine dual catalysis. The strategy is attractive and valuable because of the convenient one-step procedure, environmental friendliness, high enantioselectivity and good functionalgroup tolerance. [ABSTRACT FROM AUTHOR]

A crystalline supramolecular photocatalyst is prepared through metal‐induced self‐assembly of perylene diimide with imidazole groups at the imide position (PDI‐Hm). Exploiting the metal‐coordination ability of imidazole, a crystalline assembly of copper‐coordinated PDI‐Hm (CuPDI‐Hm) in a nanorod shape is prepared which displays an outstanding photocatalytic oxygen evolution rate of 25,900 μmol g−1 h−1 without additional co‐catalysts. The imidazole‐copper coordination, along with π–π stacking of PDI frameworks, guides the arrangement of PDI‐Hm molecules to form highly crystalline assemblies. The coordination of copper also modulates the size of the CuPDI‐Hm supramolecular assembly by regulating the nucleation and growth processes. Furthermore, the imidazole‐copper coordination constructs the electric field within the PDI‐Hm assembly, hindering the recombination of photo‐induced charges to enhance the photoelectric/photocatalytic activity when compared to Cu‐free PDI‐Hm assemblies. Small CuPDI‐Hm assembly exhibits higher photocatalytic activity due to their larger surface area and reduced light scattering. Together, the Cu‐imidazole coordination presents a facile way for fabricating size‐controlled crystalline PDI assemblies with built‐in electric field enhancing photoelectric and photocatalytic activities substantially. [ABSTRACT FROM AUTHOR]

The π-π interaction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials, while other non-covalent intermolecular interactions especially the σ-π hyperconjugation are often ignored. Herein, a perylene diimide (PDI) derivative named FIDT-PDI is designed and synthesized to shed light into the effect of hyperconjugation on the molecular packing and further the photovoltaic performance. Dynamic NMR and 2D NOE NMR demonstrate the formation of intermolecular σ-π hyperconjugation between the C--H bond of the PDI moiety in one molecule and the phenyl sidechain in another molecule of FIDT-PDI. Benefiting from the σ-π hyperconjugation, FIDT-PDI with twisted backbone reversely exhibits more ordered packing and stronger crystallinity compared with another PDI derivative FIDTT-PDI which has better planarity, consequently achieving superior PCE and higher carrier mobility. This contribution is the first paradigm to unravel the structure-property relationship between σ-π hyperconjugation of conjugated materials and corresponding photovoltaic performance. [ABSTRACT FROM AUTHOR]

The review covers publications over the past decade on new methods of synthesis of pyrrolo[3,4-b]-pyrrole-4,6(1H,5H)-diones, 4H-thieno[2,3-c]pyrrole-4,6(5H)-diones, 4H-pyrrolo[3,4-d][1,3]thiazole-4,6(5H)-di-ones, 5H-pyrrolo[3,4-b]pyridine-5,7(6H)-diones, 1H-pyrrolo[3,4-c]pyridine-1,3(2H)-diones, and other male-imide-fused heterocycles. Both methods for the construction of maleimide ring and those based on reactions of N-substituted maleimides, 3,4-dihalomaleimides, and other maleimide derivatives are considered. [ABSTRACT FROM AUTHOR]

A fused naphthodithiophene diimide (NDTI) derivative is first used as cathode interlayer materials (CIMs) in organic solar cells, by introducing two dimethylamine‐functionalized fluorenes on both sides, namely NDTI1. Meanwhile, two non‐fused naphthalene diimide (NDI) derivatives are synthesized as the control CIMs to validate the design strategy of fused NDI. All three CIMs show high thermal stability, robust adhesion, and strong electrode modification capability. Compared with two NDI‐based materials, NDTI1 possesses excellent film‐forming capacity and strong crystallinity, simultaneously. Besides, NDTI1 presents a strong self‐doping effect and distinct intermolecular interaction with non‐fullerene acceptors. As expected, the NDTI1‐based OSCs achieve a power conversion efficiency (PCE) of 18.02% using the PM6:Y6 active layer and a champion PCE of 19.01% employing the active layer PM6:L8‐BO, which is attributed to improve charge transport and extraction, and suppressive charge recombination. More importantly, NDTI1 retains 91% of the optimal PCE when the film thickness increases from 7 to 20 nm. Furthermore, NDTI1 also exhibits satisfactory universality for different active layer materials and excellent device stability. [ABSTRACT FROM AUTHOR]

The homogeneous non-catalytic hydrogenation of several types of iso- and syndiotactic cis-1,4 poly(1,3-diene)s with diimide, formed by thermal decomposition of p-toluene-sulfonyl-hydrazide, was examined. Perfectly alternating ethylene/1-alkene copolymers having different tacticity (i.e., isotactic and syndiotactic), which in some cases are difficult to synthesize by simple stereospecific co-polymerization of the corresponding monomers, were obtained. All the copolymers synthesized were fully characterized from a structural, morphological, and rheological point of view through different analytical techniques (FT-IR, NMR, GPC, DSC, RX). [ABSTRACT FROM AUTHOR]

Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes as guests into a host molecule combining benzophenone with naphthalene diimide. This approach led to the creation of fascinating fluorescence and RTP properties dependent on the guest molecules. Notably, crystals containing chlorobenzene showed cyan fluorescence, while those with iodobenzene displayed red RTP. This difference highlights the impact of the guest molecule on the luminescent properties, with the significant external heavy‐atom effect of iodobenzene playing a key role in promoting efficient intersystem crossing between the excited singlet and triplet states. Crystals with bromobenzene exhibited a unique blend of fluorescence and RTP, both from benzophenone and naphthalene diimide, highlighting the moderate heavy‐atom effect. These findings reveal composite materials with remarkably diverse and interesting optical characteristics. [ABSTRACT FROM AUTHOR]

[Display omitted] Well-defined silica-supported Ti imido complex (SiO)Ti(NBut)(Me 2 Pyr)(Py) 2 (Me 2 Pyr = 2,5-dimethyl- pyrrolyl) catalyzes condensation of N -sulfinylanilines into sulfurdiimines via the oxo/imido heterometathesis providing a convenient synthetic route to functionalized sulfurdiimines. [ABSTRACT FROM AUTHOR]

Reconfigurable soft actuators can be programmed to morph into different 3D shapes under the same stimulus exhibiting great potential for adaptive robotic functionalities. Liquid crystalline crosslinked materials programmed and controlled by light have demonstrated great potential in this area, however, their implementation is mainly based on azobenzene chromophores, using ultraviolet light that can potentially damage the device and its surroundings, especially if living cells are present. Here, an ink is presented, containing a green‐absorbing perylene diimide chromophore, to prepare light active liquid crystalline elastomer (LCE) actuators via direct ink writing. Green light irradiation of the LCE elements leads to photothermal actuation, but also to new absorption bands in the far‐red and near‐infrared, ascribed to the formation of radical species. Far‐red irradiation results in mechanical actuation and, advantageously, a recovery of the original absorption spectrum. This reversible transformation enables spatial reconfigurability of the actuator's response to far‐red light. The reconfigurable system gives access to complex deformation modes by simply exciting the element with homogeneous far‐red light, without the need for any structural modification of the actuator. This material strategy, using green and far‐red light, less harmful than ultraviolet, shows significant promise for future development of reconfigurable actuators for biomedical applications. [ABSTRACT FROM AUTHOR]

The built‐in electric field of the polymer semiconductors could be regulated by the dipole moment of its building blocks, thereby promoting the separation of photogenerated carriers and achieving efficient solar‐driven water splitting. Herein, three perylene diimide (PDI) polymers, namely oPDI, mPDI and pPDI, are synthesized with different phenylenediamine linkers. Notably, the energy level structure, light‐harvesting efficiency, and photogenerated carrier separation and migration of polymers are regulated by the orientation of PDI unit. Among them, oPDI enables a large dipole moment and robust built‐in electric field, resulting in enhanced solar‐driven water splitting performance. Under simulated sunlight irradiation, oPDI exhibits the highest photocurrent of 115.1 μA cm−2 for photoelectrochemical oxygen evolution, which is 11.5 times that of mPDI, 26.8 times that of pPDI and 104.6 times that of its counterparts PDI monomer at the same conditions. This work provides a strategy for designing polymers by regulating the orientation of structural units to construct efficient solar energy conversion systems. [ABSTRACT FROM AUTHOR]

Macrocyclic and medium‐sized ring ketones, lactones and lactams can all be made from common acryloyl imide starting materials through divergent, one‐pot cascade ring‐expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII)‐catalysed dihydoxylation, rearrangement through a four‐atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ring expansion. In the dihydroxylation series, three‐ or four‐atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control. [ABSTRACT FROM AUTHOR]

Dopamine (DA) is an important biomarker related to parkinsonism, schizophrenia and renal disease. Traditional electrochemical sensors for DA were based on the direct electrochemical oxidation of DA. In this paper, we report a new sensing strategy using N,N′-di(trimethylaminoethyl)perylene diimide (TMPDI) as an electrochemical probe and K2S2O8 as a signal enhancer for DA detection between 0 and −0.7 V with the DPV technique. MoS2 nanoflowers prepared by the hydrothermal method were used as a nanocarrier to load TMPDI. The reduction current of TMPDI was found to show a stepwise and significant increase at −0.24 V with the increase of concentration of K2S2O8 due to the continuous cycle of TMPDI molecules' electrochemical reduction and chemical oxidation. The presence of DA caused a large decrease of the reduction current of TMPDI due to the synergistic interaction of the competitive consumption of DA for K2S2O8 and the blocking effect of polyDA adhering to the electrode surface. The decreased current exhibited a linear response for DA from 10 pM to 100 μM with a detection limit of 4.1 pM and the proposed sensor showed high selectivity and excellent feasibility in human urine/serum sample detection. [ABSTRACT FROM AUTHOR]

The co‐assembly naphthalimide/perylene diimide (NDINH/PDINH) supramolecular photocatalysts were successfully synthesized via a rapid solution dispersion method. A giant internal electric field (IEF) in co‐assembly structure was built by the larger local dipole. NDINH coated on PDINH could reduce the reflected electric field over PDINH to improve its responsive activity to ultraviolet light. Resultantly, an efficient full‐spectrum photocatalytic overall water splitting activity with H2 and O2 evolution rate of 317.2 and 154.8 μmol g−1 h−1 for NDINH/PDINH together with optimized O2 evolution rate with 2.61 mmol g−1 h−1 using AgNO3 as a sacrificial reagent were achieved. Meanwhile, its solar‐to‐hydrogen efficiency was enhanced to 0.13 %. The enhanced photocatalytic activity was primarily attributed to the IEF between NDINH and PDINH, significantly accelerating transfer and separation of photogenerated carriers. Additionally, a direct Z‐Scheme pathway of carriers contributed to a high redox potential. The strategy provided a new perspective for the design of supramolecular photocatalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Tetralin‐1‐carboxamides are frequently incorporated in myriad medicinally important molecules. However, their existing synthetic routes not only suffer from some drawbacks such as tedious procedures, harsh reaction conditions, narrow substrate scope, low yields, and environmental problems, but are also based upon the elaboration of uneasily available non‐linear tetralin derivatives. Herein, we describe a metal‐ and additive‐free visible light‐induced [4+2] annulation of two simple linear starting materials, namely acrylamides and 2‐benzyl‐2‐bromocarbonyls, through a cascade C(sp3)−Br/C(sp2)−H bond cleavage, double C−C bond formation, and aromatization sequence. The developed protocol provides a convenient, efficient, and green approach to a variety of tetralin‐1‐carboxamide derivatives with good functional group compatibility. Importantly, the resulting products could also undergo the LiCl‐mediated mono‐decarboxylative cyclization process to further furnish the architecturally novel bridged polycyclic imides with excellent cis‐diastereoselectivities. [ABSTRACT FROM AUTHOR]

The synthesis of imides holds significant importance in various scientific disciplines and industrial applications due to their extensive use in biomolecules, inorganic compounds, and organic compounds. Traditional methods for imide synthesis often rely on the use of toxic or expensive oxidizing agents, limiting their sustainability and practicality. Herein, we present a green and environmentally friendly approach for the synthesis of imides from N-alkylamides using electrocatalytic oxidation with H2O as the green oxygen source. This sustainable and atom-efficient approach outperforms traditional methods by eliminating the need for toxic or expensive oxidants while simultaneously achieving high yields under mild reaction conditions. The protocol exhibits broad substrate compatibility, enabling the transformation of a wide range of N-alkyl (methyl, ethyl and cyclopropyl) amides into imides. The resulting imide products can serve as valuable building blocks for the synthesis of biologically relevant 1,2,4-triazole compounds. Furthermore, the practicality of this method is demonstrated through a gram-scale reaction, affirming its efficiency and potential for industrial applications. Our work presents a sustainable and versatile strategy for imide synthesis, aligning with green chemistry principles and sustainable manufacturing practices. [ABSTRACT FROM AUTHOR]

Solar light-powered photocatalytic reactions for highly efficient hydrogen evolution remain a formidable challenge. Herein, a hydrazine-functionalized perylene diimide derivative (HPDI) supramolecular aggregates were incorporated into a Ti3+ self-doped TiO 2 (Ti3+-TiO 2) by solvent mixing method for highly efficient photocatalytic hydrogen production. The integration of HPDI effectively minimized the electron transfer path and improved the photoelectrochemical activity through π-π stacking of perylene core and hydrogen bonding of the terminal moiety with the Ti3+-TiO 2. Further, the Ti3+-TiO 2 formed by the partial hydrolysis of titanium isopropoxide (TTIP) followed by calcination also introduces Ti3+ bound states in TiO 2 forming oxygen vacancies. It is demonstrated that HPDI with π-π stacking structure along with j-aggregation effectively improve the light absorption in the visible region. The photocatalytic studies for hydrogen production showed a successful formation of the step scheme mechanism in HPDI incorporated Ti3+-TiO 2 system and it exhibited a superior hydrogen production efficiency of 1390 μmol/g, which is four-folds higher than bare TiO 2. Thus, this work paves the way to design molecular structures as efficient photocatalysts for hydrogen production. [Display omitted] • HPDI was incorporated into Ti3+ -TiO 2 to form a Ti3+-TiO 2 /HPDI composite. • HPDI integration minimizes the electron transfer path and improves the photoelectrochemical activity. • Ti3+-TiO 2 introduces Ti3+ bound states and oxygen vacancies to the Ti3+-TiO 2 /HPDI. • HPDI with π−π stacking and j-aggregation improves light absorption in the visible region. • Achieved superior hydrogen production efficiency of 1390 μmol/g, 4 times higher than bare TiO 2. [ABSTRACT FROM AUTHOR]

Perylene diimide (PDI) and naphthalene diimides (NDIs) are compounds widely used in supramolecular structures due to their versatile and functional properties. They have high absorptions and photoluminescence capabilities, which make them ideal for electronic transition studies. Reflux method, a widely employed synthetic technique, was utilized to synthesize NDI and PDI derivatives. In this method, the respective amino acids and NTDA (naphthalene‐1,4,5,8‐tetracarboxylic dianhydride) were combined in acetic acid and the resulting mixture was subjected to reflux. This study centered on a diverse set of NDI and PDI ligands, comprising L‐ala‐NDI, B‐ala‐NDI, Gly‐NDI, Imi‐NDI, Pyr‐NDI, L‐ala‐PDI, B‐ala‐PDI, Gly‐PDI, Imi‐PDI, and Pyr‐PDI ligands. Crystal structures were obtained for three NDI ligands, while the characterization of all ligands involved several analytical techniques such as NMR, IR, UV, DFT, TD‐DFT calculations, and single‐crystal x‐ray crystallography specifically for the NDI ligands. The investigation focused on studying the electron acceptor/donor behavior of the NDI and PDI ligands, identifying their potential for charge transfer applications. Furthermore, the NLO (nonlinear optical) response of all 10 NDI and PDI ligands was assessed through an analysis involving HOMO‐LUMO, TDM, EDDM, NCI, Iso‐surface, MEP, natural population, and DOS analysis. This evaluation encompassed the examination of linear polarizability, as well as first and second hyperpolarizability in the context of NLO. The findings of the study revealed that Gly‐PDI, Imi‐PDI, L‐ala‐PDI, and B‐ala‐PDI ligands displayed a higher NLO response compared with the other ligands. These results highlight the potential of these ligands for nonlinear optical applications. The comprehensive characterization and assessment of the NDI and PDI ligands contribute to a deeper understanding of their electron properties, positioning them as promising candidates for charge transfer and nonlinear optical materials. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis and properties of a new type of dye called perimidinium imides. These dyes have tunable optical properties and can self-assemble in different solvents. The researchers synthesized two different perimidinium imides and studied their absorption and photoluminescence properties in various solvents. They found that the dyes exhibited different morphologies and optical properties depending on the solvent and concentration. The dyes also retained their emissive property in water, making them potentially useful for biological applications. [Extracted from the article]

We synthesized novel polyelectrolytes based on naphthalene diimide with quaternary amine featuring hydroxyl groups at the side chain, along with different counteranions (PF-NDIN-Br-OH and PF-NDIN-I-OH) for polymer solar cell (PSC) application as the interlayer. The polyelectrolytes establish a beneficial interface dipole through the ionic moieties and synergistic effects arising from the hydroxyl groups located at the side chain. Incorporating polyelectrolytes as the cathode interlayer resulted in an enhancement of the power conversion efficiency (PCE). The PCE of the device with PF-NDIN-Br-OH increased from 8.96% to 9.51% compared to the ZnO-only device. The best PCE was obtained with the device based on PF-NDIN-I-OH, up to 9.59% resulting from the J s c enhancement. This outcome implies a correlation between the performance of the device and the synergistic effects observed in polyelectrolytes containing hydroxyl groups in the side chain, along with larger anions when employed in PSCs. [ABSTRACT FROM AUTHOR]