In Situ Photogenerated Radicals of Hydroxyl Substituted Pyrene-Based Triphenylamines with Enhanced Transport and Free Doping/Post-Oxidation for Efficient Perovskite Solar Cells.

The high-performance hole transporting material (HTM) is one of the most important components for the perovskite solar cells (PSCs) in promoting power conversion efficiency (PCE). However, the low conductivity of HTMs and their additional requirements for doping and post-oxidation greatly limits the device performance. In this work, three novel pyrene-based derivatives containing methoxy-substituted triphenylamines units (PyTPA, PyTPA-OH and PyTPA-2OH) are designed and synthesized, where different numbers of hydroxyl groups are connected at the 2- or 2,7-positions of the pyrene core. These hydroxyl groups at the 2- or 2,7-positions of pyrene play a significantly role to enhance the intermolecular interactions that are able to generate in situ radicals with the assistance of visible light irradiation, resulting in enhanced hole transferring ability, as well as an enhanced conductivity and suppressed recombination. These pyrene-core based HTMs exhibit excellent performance in PSCs, which possess a higher PCE than those control devices using the traditional spiro-OMeTAD as the HTM. The best performance can be found in the devices with PyTPA-2OH. It has an average PCE of 23.44% (PCEmax = 23.50%), which is the highest PCE among the reported PSCs with the pyrene-core based HTMs up to date. This research offers a novel avenue to design a dopant-free HTM by the combination of the pyrene core, methoxy triphenylamines, and hydroxy groups.

Reaction of Ph2C(X)(CO2H) (X = OH, NH2) with [VO(OR)3] (R = Et, nPr): structure, magnetic susceptibility and ROP capability.

Reaction of [VO(OR)3] (R = Et, nPr) with 2,2'-diphenylglycine afforded the alkoxide-bridged dimers {[VO(OR)(µ-OR)][Ph2C(NH2)(CO2)]}2, whereas use of benzilic acid, in the presence of alkali metals, afforded 16-membered metallocycles {V8(O)4M(OR)8[Ph2C(OH)(CO2)]12} (M = <1 Na, K). For the ring systems, magnetic susceptibility data is consistent with mixed-valence vanadium with an average oxidation state of 3.5. The dimer and ring systems are capable of the ring opening polymerisation (ROP) of ε-caprolactone under N2, air, or as melts affording mostly low to medium molecular weight cyclic and linear products.

Regulable high-contrast mechanofluorochromic enhancement behaviour based on substituent effects.

Herein, a facile strategy was established to build mechanoresponsive luminogens with high sensitivity to substituents and positional effects. Even in slightly different structures, distinct optical phenomena, including fluorescence efficiency and mechano-responsive properties, were clearly present. Outstanding mechanical-induced emission enhancement (5-100 times) properties and reversibility makes for promising applications in pressure sensors and OLEDs.

Phenanthrothiophene-Triazine Star-Shaped Discotic Liquid Crystals: Synthesis, Self-Assembly, and Stimuli-Responsive Fluorescence Properties.

Lipophilic biphenylthiophene- and phenanthrothiophene-triazine compounds, BPTTn and CPTTn, respectively, were prepared by a tandem procedure involving successive Suzuki-Miyaura coupling and Scholl cyclodehydrogenation reactions. These compounds display photoluminescence in solution and in thin film state, solvatochromism with increasing solvent's polarity, as well as acidochromism and metal ion recognition stimuli-responsive fluorescence. Protonation of BPTT10 and CPTT10 by trifluoroacetic acid results in fluorescence quenching, which is reversibly restored once treated with triethylamine (ON-OFF switch). DFT computational studies show that intramolecular charge transfer (ICT) phenomena occurs for both molecules, and reveal that protonation enhances the electron-withdrawing ability of the triazine core and reduces the band gap. This acidochromic behavior was applied to a prototype fluorescent anti-counterfeiting device. They also specifically recognize Fe3+ through coordination, and the recognition mechanism is closely related to the photoinduced electron transfer between Fe3+ and BPTT10/CPTT10. CPTTn self-assemble into columnar rectangular (Colrec) mesophase, which can be modulated by oleic acid via the formation of a hydrogen-bonded supramolecular liquid crystal hexagonal Colhex mesophase. Finally, CPTTn also form organic gels in alkanes at low critical gel concentration (3.0 mg/mL). Therefore, these star-shaped triazine molecules possess many interesting features and thus hold great promises for information processing, liquid crystal semiconductors and organogelators.

Pyrene-Based Deep-Blue Fluorophores with Narrow-Band Emission.

High-efficiency narrow-band luminescent materials have attracted intense interest, resulting in their great colorimetric purity. This has led to a variety of high-tech applications in high-definition displays, spectral analysis, and biomedicine. In this study, a rigid pyrene core was employed as the molecular backbone, and four narrow-band pyrene-based blue emitters were synthesized using various synthetic methods (such as Lewis-acid catalyzed cyclization domino reactions, Pd-catalyzed coupling reactions like Suzuki-Miyaura and Sonogashira). Due to the steric effect of the hydroxy group at the 2-position, the target compounds exhibit deep blue emission (<429 nm, CIEy < 0.08) with full width at half-maximum (FWHM) less than 33 nm both in solution and when solidified. The experimental and theoretical results indicated that the substituents at the 1- and 3-positions afford a large dihedral angle with the pyrene core, and the molecular motion is almost fixed by multiple intra- and intermolecular hydrogen bonding interactions in the crystallized state, leading to a suppression of the vibrational relaxation of the molecular structure. Moreover, we observed that the suppression of the vibrational relaxation in the molecular structures and the construction of rigid conjugated structures can help develop narrow-band organic light-emitting materials.

Double-cavity cucurbiturils: synthesis, structures, properties, and applications.

Double-cavity Q[n]s are relatively new members of the Q[n] family and have garnered significant interest due to their distinctive structures and novel properties. While they incorporate n glycoluril units, akin to their single-cavity counterparts, their geometry can best be described as resembling a figure-of-eight or a handcuff, distinguishing them from single-cavity Q[n]s. Despite retaining the core molecular recognition traits of single-cavity Q[n]s, these double-cavity variants introduce fascinating new attributes rooted in their distinct configurations. This overview delves into the synthesis, structural attributes, properties, and intriguing applications of double-cavity Q[n]s. Some of the applications explored include their role in supramolecular polymers, molecular machinery, supra-amphiphiles, sensors, artificial light-harvesting systems, and adsorptive separation materials. Upon concluding this review, we discuss potential challenges and avenues for future development and offer valuable insights for other scholars working in this area with the aim of stimulating further exploration and interest.

A Coumarin-Hemicyanine Deep Red Dye with a Large Stokes Shift for the Fluorescence Detection and Naked-Eye Recognition of Cyanide.

In this study, we synthesized a coumarin-hemicyanine-based deep red fluorescent dye that exhibits an intramolecular charge transfer (ICT). The probe had a large Stokes shift of 287 nm and a large molar absorption coefficient (ε = 7.5 × 105 L·mol-1·cm-1) and is best described as a deep red luminescent fluorescent probe with λem = 667 nm. The color of probe W changed significantly when it encountered cyanide ions (CN-). The absorption peak (585 nm) decreased gradually, and the absorption peak (428 nm) increased gradually, so that cyanide (CN-) could be identified by the naked eye. Moreover, an obvious fluorescence change was evident before and after the reaction under irradiation using 365 nm UV light. The maximum emission peak (667 nm) decreased gradually, whilst the emission peak (495 nm) increased gradually, which allowed for the proportional fluorescence detection of cyanide (CN-). Using fluorescence spectrometry, the fluorescent probe W could linearly detect CN- over the concentration range of 1-9 µM (R2 = 9913, RSD = 0.534) with a detection limit of 0.24 µM. Using UV-Vis spectrophotometry, the linear detection range for CN- was found to be 1-27 µM (R2 = 0.99583, RSD = 0.675) with a detection limit of 0.13 µM. The sensing mechanism was confirmed by 1H NMR spectroscopic titrations, 13C NMR spectroscopy, X-ray crystallographic analysis and HRMS. The recognition and detection of CN- by probe W was characterized by a rapid response, high selectivity, and high sensitivity. Therefore, this probe provides a convenient, effective and economical method for synthesizing and detecting cyanide efficiently and sensitively.

Detection of basic amino acids under highly alkaline conditions using a perylene amine-derived probe.

pH plays a crucial part in numerous chemical and physiological processes. In this work, a new perylene diimide derivative that acts as a pH-sensitive dye with Bay Area Carboxylic Acid functionality. The derivative utilizes the outstanding thermal, chemical and photochemical stability found in PDI materials and has remarkable UV-visible absorption and fluorescence emission qualities. Based on these properties, a fluorescent probe (PCA) was synthesised using a perylene tetracarbodiimide (PDI) backbone for the recognition of alkaline pH. In alkaline environments where the pH values are between 10 and 14, the fluorescence intensity significantly decreases, and a blue shift occurs, which is a standard feature of alkaline pH probes. The probe demonstrates exceptional sensing ability within the pH range of 10.00-14.00, with notable stability and reversibility. Encapsulation of the probe in a thin polymer film material enhances the pH sensing capability of the system. New sensor has been developed to detect basic amino acids by utilizing the probes' pH response characteristics. this sensor has also been applied to detect the concentration of arginine.

Influence of Steric Effects on the Emission Behavior of Pyrene-Based Blue Luminogens.

Pyrene-based derivatives have been widely deployed in organic luminescent materials because of their bright fluorescence, high charge carrier mobility, and facile modification. Nevertheless, the fluorescence output of conventional pyrenes is prone to quenching upon aggregation due to extensive intermolecular π-π stacking interactions. To address this issue, a set of new Y-shaped pyrene-containing luminogens are synthesized from a new bromopyrene chemical precursor, 2-hydroxyl-7-tert-butyl-1,3-bromopyrene, where the bromo and hydroxyl groups at the pyrene core can be readily modified to obtain the target products and provide great flexibility in tuning the photophysical performances. When the hydroxy group at the 2-position of pyrene was replaced by a benzyl group, the steric hindrance of the benzyl group not only efficiently inhibits the detrimental intermolecular π-π stacking interactions but also rigidifies the molecular conformation, resulting in a narrow-band blue emission. Moreover, the TPE-containing compounds 2c and 3c possessed characteristic aggregation-induced emission (AIE) properties with fluorescence quantum yields of up to 66% and 38% in the solid state, respectively. Thus, this article has methodically investigated the factors influencing the optical behavior, such as intermolecular interactions, and the steric effects of the substituent group, thereby opening up the potential to develop narrow-band pyrene-based blue emitters for OLED device applications.

Mixed-magnesium/zinc calix[4]arene complexes: structure, and ring opening polymerisation studies.

Different combinations of organomagnesium reagents and zinc bromide react with either 1,3-dimethoxy-4-tert-butylcalix[4]areneH2 (L(OMe)2H2) or trialkoxycalix[4]arenes (L(OR)3H) (R = n-Pr, n-pentyl) to afford mixed-metal calix[4]arene systems. Intriguing molecular structures are formed and the systems are capable of the ring opening polymerisation of ε-caprolactone under N2, air, or as melts.

Double Cross-Linked Hydrogel Dressings Based on Triblock Copolymers Bearing Antifreezing, Antidrying, and Inherent Antibacterial Properties.

Bacterial infections typically invade the living tissue of wounds, thereby aggravating the inflammatory response, delaying wound healing, or causing further complications. In this paper, the antibacterial hydrogel (PNVBA) with antifreezing and antidrying properties was prepared by a two-step method using N-isopropylacrylamide (NIPAM), 1-butyl-3-vinylimidazolium bromide (VBIMBr), and 3-acrylamidophenylboronic acid (AAPBA). PNVBA hydrogels exhibited a high adsorption capacity of 280 mg·g-1 for bovine serum albumin (BSA) and can adhere to the surface of different materials through ion-dipole or hydrogen-bonding interactions. Meanwhile, the PNVBA hydrogels exhibited high viscoelasticity and good adhesion after freezing at -20 °C or heating at 70 °C for 24 h with a sterilizing rate of up to 98% against multidrug-resistant (MDR) Escherichia coli and methicillin-resistant Staphylococcus aureus (MRSA). Moreover, a survival rate of up to 90% after incubation with L929 cells over 24 h was observed. Therefore, this inherent antibacterial hydrogel can be used as an excellent alternative material for wound dressings.

New pyrrolo[3,2-b]pyrroles with AIE characteristics for detection of dichloromethane and chloroform.

Three new pyrrolo[3,2-b]pyrrole derivatives containing methoxyphenyl, pyrene or tetraphenylethylene (TPE) units (compounds 1-3) have been designed, synthesized and fully characterized. The aggregation-induced emission (AIE) properties of compounds 1-3 were tested in different water fraction (fw ) of tetrahydrofuran (THF). The pyrrolo[3,2-b]pyrrole derivative 3 containing TPE units exhibited typical AIE features with an enhanced emission (∼32-fold) in the solid state versus in solution; compounds 1 and 2 exhibited an aggregation-caused quenching effect. In addition, the steric and electronic effects of the peripheral moieties on the emission behavior, both in solution and in the solid state, have been investigated. Moreover, pyrrolo[3,2-b]pyrrole 1 exhibits high sensitivity and selectivity for dichloromethane and chloroform solvents, with the system displaying a new emission peak and fast response time under ultraviolet irradiation.

Aggregation behaviour of pyrene-based luminescent materials, from molecular design and optical properties to application.

Molecular aggregates are self-assembled from multiple molecules via weak intermolecular interactions, and new chemical and physical properties can emerge compared to their individual molecule. With the development of aggregate science, much research has focused on the study of the luminescence behaviour of aggregates rather than single molecules. Pyrene as a classical fluorophore has attracted great attention due to its diverse luminescence behavior depending on the solution state, molecular packing pattern as well as morphology, resulting in wide potential applications. For example, pyrene prefers to emit monomer emission in dilute solution but tends to form a dimer via π-π stacking in the aggregation state, resulting in red-shifted emission with quenched fluorescence and quantum yield. Over the past two decades, much effort has been devoted to developing novel pyrene-based fluorescent molecules and determining the luminescence mechanism for potential applications. Since the concept of "aggregation-induced emission (AIE)" was proposed by Tang et al. in 2001, aggregate science has been established, and the aggregated luminescence behaviour of pyrene-based materials has been extensively investigated. New pyrene-based emitters have been designed and synthesized not only to investigate the relationships between the molecular structure and properties and advanced applications but also to examine the effect of the aggregate morphology on their optical and electronic properties. Indeed, new aggregated pyrene-based molecules have emerged with unique properties, such as circularly polarized luminescence, excellent fluorescence and phosphorescence and electroluminescence, ultra-high mobility, etc. These properties are independent of their molecular constituents and allow for a number of cutting-edge technological applications, such as chemosensors, organic light-emitting diodes, organic field effect transistors, organic solar cells, Li-batteries, etc. Reviews published to-date have mainly concentrated on summarizing the molecular design and multi-functional applications of pyrene-based fluorophores, whereas the aggregation behaviour of pyrene-based luminescent materials has received very little attention. The majority of the multi-functional applications of pyrene molecules are not only closely related to their molecular structures, but also to the packing model they adopt in the aggregated state. In this review, we will summarize the intriguing optoelectronic properties of pyrene-based luminescent materials boosted by aggregation behaviour, and systematically establish the relationship between the molecular structure, aggregation states, and optoelectronic properties. This review will provide a new perspective for understanding the luminescence and electronic transition mechanism of pyrene-based materials and will facilitate further development of pyrene chemistry.

Pyrene-Based Cationic Fluorophores with High Affinity for BF4-, PF6-, and ClO4- Anions: Detection and Removal.

Anions play an indispensable role in the balance and regulation of the ecological environment and human health; however, excess anions can cause serious ecological and environment problems. Therefore, the detection and removal of excess anions in aqueous solution is not only a technological problem but also crucial for environmental protection. Herein, a set of water-soluble pyrene-based cationic fluorophores were synthesized, which exhibit high sensitivity for the detection of the anions BF4-, PF6-, and ClO4- via electrostatic interactions. Such fluorescent probes exhibit "turn-on" emission characteristics even at low concentrations of anions due to anion-π+ interactions. Moreover, these fluorescence probes act as efficient precipitating agents for the removal of the BF4-, PF6-, and ClO4- anions from an aqueous environment. This work opens up new avenues for future research on pyrene-based fluorophores as turn-on fluorescence probes for anion detection and as excellent precipitating agents in environmental settings.

Supramolecular Assembly of Tetramethylcucurbit[6]uril and 2-Picolylamine.

The supramolecular assembly of symmetrical tetramethylcucurbit[6]uril (TMeQ[6]) and 2-picolylamine (AMPy) has been investigated via various techniques, including ultraviolet-visible (UV-vis) and nuclear magnetic resonance spectroscopy, isothermal titration calorimetry (ITC), and X-ray crystallography. The results indicated that TMeQ[6] could encapsulate the AMPy guest molecule to form a stable inclusion complex. The rotational restriction of the guest in the cavity of TMeQ[6] resulted in a large negative value of entropy. The X-ray crystal structure of the 1:1 inclusion complex between TMeQ[6] and AMPy revealed that AMPy exists in the elliptical cavity of TMeQ[6].

Novel fluorescent probe for sequential recognition of Zn2+ and pyrophosphate in aqueous based on aggregation-induced emission.

A new fluorescent probe (E)-4-(4-([2,2':6',2''-terpyridin]-4'-yl)styryl)-1-dodecylpyridin-1-ium (TPy-SD), with the aggregation-induced emission (AIE) property in aqueous solution, has been synthesized and characterized. The new probe, TPy-SD exhibited excellent selectivity and sensitivity towards Zn2+ with a relatively low detection limit (1.76 × 10-7 M). The addition of Zn2+ is thought to disrupt the AIE property of TPy-SD, thereby leading to a fluorescence blue shift. Interestingly, the complex of probe TPy-SD with Zn2+ (Zn (II) TPy-SD), with molar ratio of 1:1, can be used as a simple, sensitive, and rapid means for the detection of pyrophosphates (PPi) in solution (water/DMSO = 99:1). As evidenced by transmission electron microscopy (TEM), dynamic light scattering (DLS) and fluorescence emission spectroscopy, this detection is thought to be due to the strong affinity between PPi and Zn2+, which brings out Zn2+ from the coordination cavity of chemical sensor TPy-SD, thus realizing the detection and recognition of PPi. Therefore, the new AIE fluorescent probe can be used as a dual probe for the detection of cations and anions.

Stimuli-responsive mechanically interlocked molecules constructed from cucurbit[n]uril homologues and derivatives.

Cucurbit[n]uril supramolecular chemistry has developed rapidly since 2001 when different cucurbit[n]uril homologues (Q[n]) were successfully separated in pure form. The combination of Q[n] cavity size and various types of external stimuli has given birth to numerous types of Q[n]-based mechanically interlocked molecules (MIMs), including (pseudo)rotaxanes, catenanes, dendrimers and poly(pseudo)rotaxanes. In this review article, the important advances in the field of Q[n]-based MIMs over the past two decades are highlighted. This review also describes examples of heterowheel (pseudo)rotaxanes and poly(pseudo)rotaxanes involving Q[n]s, and reflects on the opportunities and challenges of constructing Q[n]-based stimuli-responsive MIMs.

Supramolecular Room-Temperature Phosphorescent Hydrogel Based on Hexamethyl Cucurbit[5]uril for Cell Imaging.

The host-guest interaction between hexamethyl cucurbit[5]uril (HmeQ[5]) and 1,4-diaminobenzene (DB) was investigated, and a new low-molecular-weight supramolecular gel was prepared by a simple heating/mixing cooling method. The structure and properties of the supramolecular gel were characterized. Results revealed that DB molecules did not enter the cavity of HmeQ[5] and that hydrogen bonding between the carbonyl group at the HmeQ[5] port and the DB amino groups, together with dipole-dipole interactions and outer wall interactions, were the main driving forces for the formation of the supramolecular gel. The HmeQ[5]/DB gel system exhibits temperature sensitivity. The phosphor 6-bromo-2-naphthol (BrNp) was embedded in the gel to give the gel fluorescent phosphorescence double emission. The double emission ability at room temperature can be attributed to the ordered microstructure of the supramolecular gel, which effectively avoids the nonradiative transition of BrNp. Meanwhile, HmeQ[5]/DB-BrNp has good biocompatibility and low biotoxicity, which is compatible with HeLa cells to achieve cytoplasmic staining of HeLa in the red channel. The supramolecular gels constructed by this supramolecular assembly strategy not only have good temperature sensitivity but also extend the application of Q[n]s in biomedical fields.

Facile fluorescent detection of o-nitrophenol by a cucurbit[8]uril-based supramolecular assembly in aqueous media.

The efficient and selective detection of isomers is an attractive but challenging area. In this study, a supramolecular fluorescent probe based on cucurbit[8]uril (Q[8]) and a pyrene-based derivative (G) was prepared, which effectively recognized and removed o-nitrophenol (o-NP) from a mixture of nitrophenol isomers. The newly designed probe G@Q[8] was characterized by NMR spectroscopy, fluorescence emission and UV-Vis spectroscopy, and its host-guest properties in aqueous solution were investigated. The results revealed that the system forms a stable inclusion complex with a stoichiometric ratio of 1:1, which was accompanied by a distinct fluorescence enhancement of G. Moreover, it was employed for the rapid detection of nitrophenol isomers where o-NP showed a dramatical quenching efficiency with a detection limit of 1.53 × 10-7 mol·L-1. This highly efficient supramolecular fluorescent probe offers a new strategy for the convenient detection and removal of o-NP from mixtures in aqueous medium.

One-Pot Synthesis of Pyreno[2,1-b]furan Molecules with Two-Photon Absorption Properties.

The development of large π-conjugated polycyclic heteroaromatic materials is of immense interest, both in the academic as well as the industrial community. Herein, we present the efficient one-pot synthesis of novel pyreno[2,1-b]furan molecules from a newly designed intermediate, which display intense green emission (505-516 nm) in solution and a large red shift emission (625-640 nm) in the solid state, because of strong π-π stacking. More interestingly, the compounds exhibit novel two-photon absorption (TPA) properties, and the TPA cross-section (δ) value was increased to 533 GM by regulating the electronic effects of the substituents of the pyreno[2,1-b]furan molecules. This study not only offers a facile strategy for constructing new pyrene-fused luminescence materials with two-photon absorption properties but also provides a new chemical intermediate that opens up a new pathway to advanced materials.