Supramolecular Room Temperature Phosphorescent Materials Based on Cucurbit[8]uril for Dual Detection of Dodine.

In recent years, host-guest interactions of macrocycles have attracted much attention as an emerging method for enhancing the intersystem crossing of pure organic room-temperature phosphorescence. In this work, we utilize cucurbit[8]uril (Q[8]) to specifically recognize synthetic bromophenyl pyridine derivatives (BPCOOH) to construct a highly stable charge-transfer dimer, where the bromophenyl pyridine moiety of BPCOOH is encapsulated by Q[8] in a 1:2 host/guest ratio. The assemblies exhibit specific recognition and detection properties for dodine on both fluorescence and phosphorescence spectra. Subsequently, the solid films were prepared by introducing carboxymethylcellulose sodium into the assemblies, which greatly enhanced its RTP performance by increasing the noncovalent bonding interactions, enabling the visualization of high-strength RTP and quantitative testing of the solid state. Finally, this material was used for the application of portable indicator papers to achieve rapid and visualized detection of dodine in daily life, which provides more possibilities for the potential applications of cucurbit[n]uril-based room-temperature phosphorescence material.

Hierarchical Supramolecular Self-Assembly: Fabrication and Visualization of Multiblock Microstructures.

Due to the fast dynamics and re-equilibration of supramolecular self-assembly, bottom-up molecular strategies to fabricate well-defined and controllable multiblock structures are rare. Herein, we propose a new concept for fabrication of fluorescent multiblock microcolumns containing 1 to 7 blocks via hierarchical supramolecular self-assembly based on cucurbit[8]uril (CB[8]), NaBr and an AIEgen guest. Through the complexation between CB[8] and different numbers of AIEgen guests (2, 1, 0), the competitive displacement caused by the binding of the sodium cation to the CB[8] portal, and the reversible assembly of positively charged guests in salt solutions, one-pot hierarchical supramolecular self-assembly is realized. The molecular structure of each block is analyzed by single-crystal X-ray diffraction. The AIEgen enables the self-assembly of multiblocks to be visualized, understood, and regulated.

Cucurbit[7]uril-Encapsulation-Controlled Supramolecular Photoproduct and Radical Fluorescence Emission.

Herein, a host-guest interaction-controlled photoproduct created by using cucurbit[7]uril (Q[7])-based pseudorotaxane structures is reported. The assembly exhibited controlled behavior towards the reduction of the ethylene (C=C) bond in the tetrakis(pyridin-4-yl)ethylene (TPyE) guest molecule under UV light irradiation. This can be attributed to the Q[7] encapsulation masking the four pyridinium arms of the guest, which inhibits planarization of the TPyE core to form the cyclization product. In particular, the strong affinity of Q[7] for the butyl-substituted guest (TPyE-4C) led to an unusual radical fluorescence emission of the photoirradiation-triggered intermediate of the guest molecule being observed in aqueous solution. This work provides a valuable paradigm and new insight for macrocycle-based host-guest interactions in supramolecular catalysis and luminescent radical materials.

Supramolecular Polymeric Material Based on Twisted Cucurbit[14]uril: Sensitive Detection and Removal of Potential Cyanide from Water.

Potassium ferricyanide in an aqueous solution is easily decomposed into highly toxic substances (potassium cyanide and hydrogen cyanide) by light or alkaline action, which poses a major hazard to environmental and human health. Here, a reticulated aggregation-induced emission (AIE) supramolecular polymer material (TPAP-Mb@tQ[14]) was prepared by the supramolecular self-assembly of twisted cucurbit[14]uril (tQ[14]) and a triphenylamine derivative (TPAP-Mb). TPAP-Mb@tQ[14] not only recognizes Fe(CN)63- with sensitive specificity with a limit of detection (LOD) of 1.64 × 10-7 M but can also effectively remove and adsorb Fe(CN)63- from an aqueous solution with a removal rate as high as 97.38%. Meanwhile, an important component of the supramolecular polymer material (tQ[14]) can be reused. Thus, the tQ[14]-based supramolecular assembly has the potential to be used for applications addressing toxic anionic contaminants present in aqueous environments.

A New Cationic Fluorescent Probe for HSO3- Based on Bisulfite Induced Aggregation Self-Assembly.

In comparison with the numerous studies that have centered on developing molecular frameworks for the functionalization of fluorescent materials, less research has addressed the influence of the side chains, despite such appendages contributing significantly to the properties and applications of fluorescent materials. In this work, a new series of cationic fluorescent probes with AIE characteristics have been developed, which exhibit unique sensitivity for charge-diffusion anions, namely HSO3-, via the interactions of ions and the cooperation of the controllable hydrophobicity. The impact of the alkyl chain length attached at the cationic probes suggested that the fluorescent intensity and sensitivity of the probes could be partially enhanced by adjusting their aggregation tendency through the action of the hydrophobic effect under aqueous conditions. DLS and SEM images indicated that different particle sizes and new morphologies of the probes were formed in the anion-recognition-triggered self-assembly process, which could be attributed to the composite effect of electrostatic actions, Van der Waals forces and π-π stacking.

Assembly and Applications of Macrocyclic-Confinement-Derived Supramolecular Organic Luminescent Emissions from Cucurbiturils.

Cucurbit[n]urils (Q[n]s or CB[n]s), as a classical of artificial organic macrocyclic hosts, were found to have excellent advantages in the fabricating of tunable and smart organic luminescent materials in aqueous media and the solid state with high emitting efficiency under the rigid pumpkin-shaped structure-derived macrocyclic-confinement effect in recent years. This review aims to give a systematically up-to-date overview of the Q[n]-based supramolecular organic luminescent emissions from the confined spaces triggered host-guest complexes, including the assembly fashions and the mechanisms of the macrocycle-based luminescent complexes, as well as their applications. Finally, challenges and outlook are provided. Since this class of Q[n]-based supramolecular organic luminescent emissions, which have essentially derived from the cavity-dependent confinement effect and the resulting assembly fashions, emerged only a few years ago, we hope this review will provide valuable information for the further development of macrocycle-based light-emitting materials and other related research fields.

Cucurbit[8]uril-Assisted Nucleophilic Reaction: A Unique Supramolecular Approach for Cyanide Detection and Removal from Aqueous Solution.

A unique supramolecular approach of preparing and using a cucurbit[8]uril (Q[8])-based dynamic host-guest assembly for cyanide sensing in and removal from water has been successfully developed. The dicyanovinyl-attached cationic guest (1) was designed as the fluorescent response moiety for the detection of the cyanide anion via a nucleophilic addition reaction in the assist of the Q[8]-based 2:2 quaternary complexes. Furthermore, the reaction of cyanide with 1 further switched the Q[8]-based host-guest assemblies from the 2:2 complexes to the 1:1 supramolecular polymers that precipitate in water. Thus, the macrocyclic-based dynamic host-guest assembly has potential use in applications for solving the problem of toxic anion pollutants present in aqueous environments.

An Air-Stable Organic Radical from a Controllable Photoinduced Domino Reaction of a Hexa-aryl Substituted Anthracene.

Air-stable organic radicals and radical ions have attracted great attention for their far-reaching application ranging from bioimaging to organic electronics. However, because of the highly reactive nature of organic radicals, the design and synthesis of air-stable organic radicals still remains a challenge. Herein, an air-stable organic radical from a controllable photoinduced domino reaction of a hexa-aryl substituted anthracene is described. The domino reaction involves a photoinduced [4 + 2] cycloaddition reaction, rearrangement, photolysis, and an elimination reaction; 1H/13C NMR spectroscopy, high resolution mass spectrometry, single-crystal X-ray diffraction, and EPR spectroscopy were exploited for characterization. Furthermore, a photoinduced domino reaction mechanism is proposed according to the experimental and theoretical studies. In addition, the effects of employing push and pull electronic groups on the controllable photoinduced domino reaction were investigated. This article not only offers a new blue emitter and novel air-stable organic radical compound for potential application in organic semiconductor applications, but also provides a perspective for understanding the fundamentals of the reaction mechanism on going from anthracene to semiquinone in such anthracene systems.

Cucurbit[10]uril-Encapsulated Cationic Porphyrins with Enhanced Fluorescence Emission and Photostability for Cell Imaging.

Porphyrins are widely applied for imaging, diagnosis, and treatment of diseases because of their excellent photophysical properties. However, porphyrins easily tend to aggregate driven by hydrophobic interaction and π-π stacking in an aqueous medium, which causes fluorescence quenching of the porphyrins as well as limitation of cell uptake and intracellular accumulation. Herein, cucurbit[10]uril (CB[10]) was used to fully encapsulate cationic porphyrin (CPor) in the large cavity with strong binding affinity in aqueous solutions, and the CPor aggregates were efficient disassembled, companying remarkable enhancing its fluorescence intensity. The CB[10]-based host-guest complex provided excellent protection to CPor, resulting in less susceptibility to oxidation and imparting higher photostability to CPor for cell imaging. In addition, by complexation with CB[10], it was found that the fluorescence signals and photostability of CPor were also effectively improved in cells with different reactive oxygen species levels. It is highly anticipated that the large macrocyclic host cavity-triggered large-guest encapsulation strategy in this work will provide a convenient and efficient method for designing supramolecular porphyrin dyes, thus broadening the diagnosis and imaging application in cells and microorganisms.

Cucurbit[n]uril-Based Supramolecular Frameworks Assembled through Outer-Surface Interactions.

Porous materials, especially metal-organic frameworks, covalent organic frameworks, and supramolecular organic frameworks, are widely used in heterogeneous catalysis, adsorption, and ion exchange. Cucurbit[n]urils (Q[n]s) suitable building units for porous materials because they possess cavities with neutral electrostatic potential, portal carbonyls with negative electrostatic potential, and outer surfaces with positive electrostatic potential, which may result in the formation of Q[n]-based supramolecular frameworks (QSFs) assembled through the interaction of guests within Q[n]s, the coordination of Q[n]s with metal ions, and outer-surface interaction of Q[n]s (OSIQ). This review summarizes the various QSFs assembled via OSIQs. The QSFs can be classified as being assembled by 1) self-induced OSIQ, 2) anion-induced OSIQ, and 3) aromatic-induced OSIQ. The design and construction of QSFs with novel structures and specific functional properties may establish a new research direction in Q[n] chemistry.

Twisted Schiff-base macrocycle showing excited-state intramolecular proton-transfer (ESIPT): assembly and sensing properties.

A Schiff-base macrocyclic host (MH) showing ESIPT and AIEE is reported for the first time; the fluorescent macrocycle exhibited good pH tolerance and could serve as a probe for Cu2+ and Fe3+ ion sensing and removal. In addition, a series of size-tunable nanoparticles was fabricated by the self-assembly of free MH and its coordination complex with Fe3+ in THF/water solution.

Tuning the amphiphilicity of terpyridine-based fluorescent probe in water: Assembly and disassembly-controlled H g2+ sensing, removal, and adsorption of H2S.

A water-soluble terpyridine-based cationic fluorescent probe (SP-TPy) was synthesized, which emerged with pH-dependent amphiphilicity, resulting in self-assembly and disassembly in aqueous media with the aggregation-induced emission (AIE) property. In neutral water (pH 7.4), a moderate sensing response to Hg2+ ions was given by the self-assembly of SP-TPy. However, in acidic aqueous media, the monomer of SP-TPy not only appeared to be highly selective and sensitive for Hg2+ ions, but also displayed highly efficient removal of Hg2+ ions from solution by rapid precipitation, which was attributed to the coordination-triggered reassembly of SP-TPy. The removal efficiency of SP-TPy for Hg2+ was found to be over 99%. Further study indicated that the precipitates were composed of various polyhedral porous frameworks, a property that was further used to adsorb H2S gas to form HgS complexes with higher uptake capacities. In addition, SP-TPy can be efficiently regenerated and recycled using a simple treatment with acidic water after adsorption of the H2S gas.

Fabrication of nor-seco-cucurbit[10]uril based supramolecular polymers via self-sorting.

A nor-seco-CB[10] (ns-CB[10]) based linear supramolecular polymer is firstly fabricated via self-sorting strategy. Through self-sorting of the monomer, ns-CB[10] and CB[7], the unfavorable factors for supramolecular polymerization are avoided. Therefore, supramolecular polymer with high molecular weight is successfully fabricated, and the molecular weight can be controllably regulated.

Cucurbit[7]uril-anchored polymer vesicles enhance photosensitization in the nucleus.

Effective photosensitizers (PSs) are highly desirable in many applications, such as photodynamic therapy and catalytic chemistry. Here, we demonstrated that vesicles of cucurbit[7]uril (Q[7] or CB[7])-anchored polymers enhanced photosensitization in the nucleus. The polyacrylic acid chain spacer triggered Q[7] polymers on the surfaces of the vesicles at a regular distance, thus not only leading to efficient inhibition of the aggregation induced self-quenching of the porphyrin based cationic PS in aqueous solution but also maintaining the PS at high concentration on the nanoscale via stable host-guest interactions. Further experiments indicated that Q[7] polymer based vesicles as a PS loading vehicle had a high penetration depth, entering the nuclei of cancer cells. Therefore, highly enhanced photosensitization and efficient anticancer effects were achieved.

Host-guest interactions in nor-seco-cucurbit[10]uril: novel guest-dependent molecular recognition and stereoisomerism.

The unique monomer and excimer fluorescence emissions of pyrene were first exploited as distinctly photophysical signals to identify the possible diastereomers of guests within nor-seco-cucurbit[10]uril (NS-CB[10]) cavities. Further experiments revealed that balancing the hydrophilic and hydrophobic effects of the guest in aqueous solution can improve the molecular recognition and binding ability of NS-CB[10].

Organic core-shell-shaped micro/nanoparticles from twisted macrocycles in Schiff base reaction.

Functional self-assemblies derived from noncovalent interactions such as lipid vesicles and DNA chiral double helices are a typical feature of natural life activity. Because of this phenomenon, a self-assembly approach for various functional organic particles is a desirable objective in supramolecular chemistry. Here, we report the discovery of enantiomeric conformers from a twisted macrocyclic host (MH), which was obtained from an achiral precursor by Schiff base reaction. Further studies suggest that a series of unexpected and stable core-shell-based organic micro/nanospheres can be directly precipitated from a simple reaction solution with high yield. A single-crystal X-ray diffraction analysis of MH revealed that the unusual C-H···π interaction triggered self-assembly of the enantiomeric forms in the solid state plays an important role in the formation of the core-shell-shaped organic particles.

Solvent-Switched Schiff-Base Macrocycles: Self-Sorting and Self-Assembly-Dependent Unconventional Organic Particles.

Organic reaction is a powerful and versatile tool for the creation of various new substrates and materials. However, there have been few reports of the direct fabrication of organic particles by organic reactions. Herein, we report that water as a co-solvent can efficiently switch a [2 + 2] macrocycle (3) to a [1 + 1] macrocycle (4) in a Schiff-base reaction from the same precursors at room temperature. Unexpectedly, a series of tunable organic micro/nanoparticles, including solid microspheres, core-shell spheres, and vesicles, could be directly precipitated in one-step from the reaction medium with high yield. X-ray structure analysis and other characterizations indicated that social self-sorting and narcissistic self-sorting of the macrocyclic frameworks of 3 and 4 through noncovalent interactions play crucial roles in the formation of such organic particles. Most interestingly, the facile and mild fabrication conditions of the particles allowed us to accurately and in situ monitor their intermediate formation by controlling the reaction time. This work thus provides an advancement of the fabrication of tunable organic particles.

Exploration of biocompatible AIEgens from natural resources.

Luminogens with aggregation-induced emission (AIEgens) characteristics have been well developed and applied in various areas such as bio-imaging, theranostics, organic photoelectronics and chemo/bio sensors. However, most of the reported AIEgens suffer from the disadvantages of complex organic synthesis and high cost, as well as being environmentally unfriendly and hard to degrade, which have largely limited their real applications. In this work, we discovered berberine chloride, a natural isoquinoline alkaloid isolated from Chinese herbal plants, as an unconventional rotor-free AIEgen with bright solid-state emission and water-soluble characteristics. Single crystal structure analysis and optical property, viscosity, and host-guest interaction studies suggested that intramolecular vibration and twisted intramolecular charge transfer were responsible for the AIE phenomenon of berberine chloride. Moreover, berberine chloride was biocompatible and could specifically target lipid droplets in a fluorescence turn-on and wash-free manner, demonstrating the great potential of natural products as promising AIE probes.

White Light Emission from Cucurbituril-Based Host-Guest Interaction in the Solid State: New Function of the Macrocyclic Host.

Energy transfer and interchange are central for fabricating white light-emitting organic materials. However, increasing the efficiency of light energy transfer remains a considerable challenge because of the occurrence of "cross talk". In this work, by exploiting the unique photophysical properties of cucurbituril-triggered host-guest interactions, the two complementary luminescent colors blue and yellow for white light emission were independently obtained from a single fluorophore dye rather than energy transfer. Further study suggested that the rigid cavity of cucurbiturils efficiently prevented the aggregation of the dye and improved its thermal stability in the solid state by providing a regular nanosized fence for each encapsulated dye molecule. As a result, a novel macrocycle-assisted supramolecular approach for obtaining solid, white light-emitting organic materials with low cost, high efficiency, and easy scale-up was successfully demonstrated.

Host-Guest Interaction of Cucurbit[8]uril with N-(3-Aminopropyl)cyclohexylamine: Cyclohexyl Encapsulation Triggered Ternary Complex.

The host-guest interaction of a series of cyclohexyl-appended guests with cucurbit[8]uril (Q[8]) was studied by ¹H NMR spectroscopy, isothermal titration calorimetry (ITC), and X-ray crystallography. The X-ray structure revealed that two cycloalkane moieties can be simultaneously encapsulated in the hydrophobic cavity of the Q[8] host to form a ternary complex for the first time.