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As an important organic photo-functional material, spirooxazine usually does not exhibit photochromism in the solid state since the intermolecular π-π stacking impedes photoisomerization. Developing photochromic spirooxazine in the solid state is crucial for practical applications but is still full of challenges. Here, we design and synthesize a series of spirooxazine derivatives (SO1-SO4) with bulky aromatic substituents at the 4- and 7-positions of the skeleton, providing a large volume for them to undergo solid-state photochromism under mild conditions. All compounds SO1-SO4 exhibit tunable solid photochromism without ground colors, excellent fatigue resistance, and high thermal stability. Notably, it takes only 15 s for SO4 to reach the saturation of absorption intensity, representing the fastest solid-state photoresponse of spirooxazines to the best of our knowledge. X-ray crystal structures of the intermediate compound SO0 and the products SO1-SO2 as well as the computational studies suggest that the bulky aromatic groups can lead to a hypochromic effect, allowing for the photochromism of SO in the solid state. The ideal photochromic properties of these spirooxazines open a new avenue for their applications in UV printing, Quick Response (QR) code, and related fields. This article is protected by copyright. All rights reserved.

This review discusses the design and syntheses of molecular-scale pillar[n]arene-based porous materials with promising applications and summarises the development of using pillar[n]arenes as the building blocks of porous materials. From the perspective of 'role of participation' in the syntheses of molecular-scale pillar[n]arene-based porous materials, the content can be divided into pillar[n]arenes serving as supramolecular nanovalves on surfaces and as ligands for metal-organic frameworks and covalent organic polymers. By integrating pillararenes, which possess rigid pillar-like structures, electron-rich cavities and desirable host-guest properties, with porous polymers of large surface areas and abundant active sites, applications of the resulting materials in drug release platforms, molecular recognition, sensing, detection, gas adsorption, removal of water pollution, organic photovoltaic materials and heterogeneous catalysis can be realised simultaneously and efficiently. Finally, in the conclusion and prospect part, we put forward the challenges and viewpoints of the current research on pillar[n]arene-based porous materials. We hope this article can provide a timely and valuable reference for researchers interested in synthetic macrocycles and porous materials.

Summary Supramolecular macrocyclic compounds including cyclodextrin, pillararene, calixarene, and cucurbituril are a family of multifarious hosts capable of selectively binding with guests via their intrinsic cavities. They have been used as ideal functional entities on the surface of inorganic nanoparticles to improve their solubility, stability, and biocompatibility in vivo. Macrocyclic compounds can be attached onto the surface of inorganic nanoparticles via covalent or noncovalent bonds, thus acting as a versatile anchoring point, which allows reversible complexation with small molecules via host-guest recognitions. A variety of functional tags including imaging probes, targeting groups, and therapeutic agents can be introduced for further functionalization of the organic-inorganic hybrid nanoparticles. The macrocycles-based organic-inorganic nanohybrids have shown remarkable properties and significant potential in various biomedical applications thanks to the surface modification of macrocycles. Here, we review the versatile construction of macrocycles-based hybrid nanomaterial platforms and discuss their significant potential in biomedical and related applications.

Photo-assisted therapy has been an advancing branch in the fields of modern theranostics and nanomedicine, holding observable superiorities such as noninvasiveness, deep tissue penetration, and spatial precision. Aggregation-induced emission luminogens (AIEgens) have emerged as powerful fluorescent materials and organic optical agents capable of performing therapeutic effects under light activation. In this review, we underscore the elaborate design and fabrication of AIEgen-based supramolecular materials for applications in the scope of photo-assisted therapy, including photothermal therapy, photodynamic therapy, and photo-induced reactions. With the aid of supramolecular self-assembly, AIE materials are endowed with higher biocompatibility, better specificity, external stimuli responsiveness, and integrated functionalities. AIEgen-based self-assembled materials categorized by different supramolecular driving forces are summarized with their respective features in both structures and therapeutic effects fully described. With these highly adjustable physicochemical properties of supramolecular assemblies, the functions of such AIE materials can be considerably expanded and optimized, also opening up possibilities for controllable multimodal theranostics. In the conclusion part, perspectives and remaining challenges in this research area are discussed.

Multifunctional supramolecular nanoplatforms that integrate the advantages of different therapeutic techniques can trigger multimodal synergistic treatment of tumors, thus representing an emerging powerful tool for cancer therapeutics. Methods: In this work, we design and fabricate a multifunctional supramolecular drug delivery platform, namely Fa-mPEG@CP5-CuS@HMSN-Py nanoparticles (FaPCH NPs), consisting of a pyridinium (Py)-modified hollow mesoporous silica nanoparticles-based drug reservoir (HMSN-Py) with high loading capacity, a layer of NIR-operable carboxylatopillar[5]arene (CP5)-functionalized CuS nanoparticles (CP5-CuS) on the surface of HMSN-Py connected through supramolecular host-guest interactions between CP5 rings and Py stalks, and another layer of folic acid (Fa)-conjugated polyethylene glycol (Fa-PEG) antennas by electrostatic interactions capable of active targeting at tumor lesions, in a controlled, highly integrated fashion for synergistic chemo-photothermal therapy. Results: Fa-mPEG antennas endowed the enhanced active targeting effect toward cancer cells, and CP5-CuS served as not only a quadruple-stimuli responsive nanogate for controllable drug release but also a special agent for NIR-guided photothermal therapy. Meanwhile, anticancer drug doxorubicin (DOX) could be released from the HMSN-Py reservoirs under tumor microenvironments for chemotherapy, thus realizing multimodal synergistic therapeutics. Such a supramolecular drug delivery platform showed effective synergistic chemo-photothermal therapy both in vitro and in vivo. Conclusion: This novel supramolecular nanoplatform possesses great potential in controlled drug delivery and tumor cellular internalization for synergistic chemo-photothermal therapy, providing a promising approach for multimodal synergistic cancer treatment.

Pillar[5]arene tetramers with tetraphenylethene cores and different lengths of alkyl ether chains (H1-4C4P and H2-2C4P) and a 9,10-distyrylanthrace-bridged neutral guest linker (DSA-G) are synthesized to fabricate tunable solid-state fluorescent materials through supramolecular assemblies of DSA-G⊂H1-4C4P and DSA-G⊂H2-2C4P. Their fluorescence emission is strongly enhanced and their colors are changed upon assembly, which can be ascribed to the supramolecular assembly-induced enhanced emission and Forster resonance energy transfer (FRET) processes between H1-4C4P (or H2-2C4P) and DSA-G. Both ensembles of DSA-G⊂H1-4C4P and DSA-G⊂H2-2C4P exhibit thermo and solvent dual-responsive features, while DSA-G⊂H2-2C4P shows higher sensitivity toward external stimuli as compared to DSA G⊂H1-4C4P due to the shorter distance between fluorophores. The use of these fluorescent materials as inks confirms their efficiencies in the solid-state, paving the way for new potential applications of smart optical materials based on supramolecular assemblies.

A dicarboxylatopillar[5]arene (DCP5)-based coordination polymer, namely DCP5-EuxTby, with color-tunable emission and capable of nitroaromatic pollutant detection, has been designed and fabricated via a typical metal–ligand coordination approach. Due to its rigid skeleton and electron-rich cavity, DCP5 plays an important role in this multi-color framework, not only as a linker but also as a blue-color fluorescence donor. Intriguingly, the fluorescent color of DCP5-EuxTby can be tuned from green to red simply by mediating the molar ratio of Eu3+ : Tb3+ in the functional system. More importantly, a white-color emitting system, that is, DCP5-Eu1Tb3, is discovered when the ratio of Eu3+ : Tb3+ is 1 : 3, and the white-light emissive DCP5-Eu1Tb3 exhibits good detection performance toward nitroaromatic pollutants in a wide application field. We envision that this work will open a new avenue for the exploration of synthetic macrocycle-based new materials in the construction of new fluorescent sensors and detectors for environmental sustainability and bio-related fields.

Organic luminescent materials with high quantum yields and/or white-light-emitting properties in particular play a crucial role in labeling and optoelectronic devices. In this work we have synthesized a new 2,3,6,7-tetramethoxy-9,10-di-p-tolylanthracene-bridged pillar[5]arene dimer with persistent mazarine blue fluorescent emission and much higher quantum yields in both solution and the solid state in comparison with its corresponding emissive linker without pillarene units, which exhibits typical aggregation-caused quenching. According to the fluorescence data and single-crystal analyses, their contrasting fluorescent performances can be rationally ascribed to their different stacking structures and intermolecular interactions. Three fluorescent guests containing different chromophores and/or terminal binding sites have also been synthesized to interact with the pillar[5]arene dimer to construct supramolecular ensembles with highly controllable luminescence, taking advantage of the stimuli-responsive properties of the supramolecular host-guest interactions. Intriguingly, multicolor fluorescence, including white-light emission (0.31, 0.35), which is in high demand, has been achieved by tuning the molar ratio of the host and guest and/or by changing the solvent system. This strategy holds great potential for the design and development of fluorescent materials with high quantum yields, controllable emission wavelength, and good stimuli-responsiveness.

A luminescent molecular crystal (P5bipy) and a Cu(I)-coordinated luminescent nanocrystal (Cu(I)-P5bipy) have been prepared concurrently using one conjugated pillar[5]arene macrocycle via a facile supramolecular self-assembling strategy. The molecular crystal shows enhanced luminescence compared with unmodified pillar[5]arene, attributed to its conjugated structure and staggered packing mode, while the coordination nanocrystal exhibits well-defined crystalline structures and long-lifetime triplet state emission along with pronounced solvochromic features.

Synthetic fungicides have been widely used to protect crops from fungal diseases. However, excessive use of synthetic fungicides leads to the generation of fungicide resistance in fungal pathogens. Recently, smart cargo delivery systems have been introduced for the construction of a pesticide delivery nanoplatform, benefiting from their controlled release performance. Herein, a fungal pathogen microenvironment-responsive supramolecular fungicide nanoplatform has been designed and constructed, using quaternary ammonium salt (Q)-modified mesoporous silica nanoparticles (MSN-Q NPs) as nanocarriers loaded with berberine hydrochloride (BH) and carboxylatopillar[5]arene (CP[5]A) as nanogates to form BH-loaded CP[5]A@MSN-Q NPs for effective inhibition of Botrytis cinerea. CP[5]A as nanogates can endow the fungicide nanoplatform with pH stimuli-responsive release features for the control of fungicide release. The loaded BH, as a natural plant fungicide, provides an ecofriendly alternative to synthetic fungicides for controlling B. cinerea. Interestingly, we use oxalic acid (OA) secreted by B. cinerea as a trigger so that BH can be released from the fungicide nanoplatform on demand under pathogen microenvironments for controlling B. cinerea. The experimental results indicate that the fabricated fungicide nanoplatform could effectively inhibit the mycelial growth and spore germination, providing a new way for the management of B. cinerea in actual application.

Room temperature phosphorescence (RTP) has attracted broad attention due to their long lifetimes, large Stokes shift, and widespread applications. Achieving RTP emission has long been a challenging task under common conditions, for the necessary requirements of promoting intersystem crossing processes and suppressing nonradiative transitions are always tough to meet. Over the past decade, RTP has been obtained through several specific strategies, among which an important method lies in immobilizing phosphors into polymer matrices. Via the effect of steric overcrowding exerted by the polymeric structures, the phosphorescence of the initial phosphors can be promoted significantly. Hence, polymer-based pure organic materials have proved to be one newly emerging subject in the field of RTP materials. In this review article, the progresses of polymer-based pure organic room temperature phosphorescent materials are elaborated from four main approaches, including doped polymer systems, copolymer systems, homopolymer systems, and host-guest complexation systems, whereby the design principles, synthesis methods, possible mechanisms, and applications are summarized and discussed in detail.

Enhanced emission and adjustable wavelength for single luminogen systems are highly desirable in the scope of photoluminescent materials. Herein, a supramolecular strategy has been proposed for supramolecular assembly-induced enhanced emission and valid emission manipulation by fabricating an amphiphilic copolymer host material with pillar[5]arene units as the side chains, whereby cyanovinylene-based (CV) derivatives are anchored to the polymer hosts via host-guest interactions. The guest-bearing copolymers can further form luminescent supramolecular polymer nanoparticles (SPNs). Remarkably, the as-prepared SPNs exhibit dramatic emission enhancement and tunable fluorescence wavelength, ascribing to the synergetic effects involving the restriction of intramolecular motions and the prevented excimer formation for CV moieties, as endowed by host-guest interactions and the entanglement of the polymer chains. Furthermore, the SPNs can be established as efficient artificial light-harvesting systems via the inclusion of Nile red into the particles for broadened emission spectra. As a proof-of-concept study, the use of pillar[5]arene-containing polymer hosts largely facilitates the emission enhancement and wavelength adjustment for the inherent luminogens, setting the basis for the supramolecular design of highly tunable luminescent systems.

Tunable luminescent materials are becoming more and more important owing to their broad application potential in various fields. Here we construct a pillar[5]arene-based hybrid material with stimuli-responsive luminescent properties and ion-sensing abilities from a pyridine-modified conjugated pillar[5]arene and a planar chromophore oligo(phenylenevinylene) upon coordination of Cd (II) metal cores. This new material not only shows an optimized luminescence due to the minimized π–π stacking and efficient charge transfer properties benefitting from the existence of pillar[5]arene rings, but also exhibits tunable multicolor emission induced by different external stimuli including solvent, ions and acid, indicating great application potential as a fluorescent sensory material, especially for Fe3+. With this pillar[5]arene-based dual-ligand hybrid material, valid optimization and regulation on the fluorescence of the original chromophore have been achieved, which demonstrates a plausible strategy for the design of tunable solid-state luminescent materials and also a prototypical model for the effective regulation of fluorescent properties of planar π systems using synthetic macrocycle-based building blocks., For higher tunability, brighter emission, and extra colors of luminescent materials, one can simply use some pillars (pillar[n]arenes) to facilitate material construction.

With the rapid development of supramolecular chemistry and nanomaterials, supramolecular nanotheranostics has attracted remarkable attention owing to the advantages compared with conventional medicine. Supramolecular architectures relying on non-covalent interactions possess reversible and stimuli-responsive features; endowing supramolecular nanotheranostics based on supramolecular assemblies great potentials for the fabrication of integrated novel nanomedicines and controlled drug delivery systems. In particular, pillarenes, as a relatively new class of synthetic macrocycles, are important candidates in the construction of supramolecular therapeutic systems due to their excellent features such as rigid and symmetric structures, facile substitution, and unique host-guest properties. This review summarizes the development of pillarene-based supramolecular nanotheranostics for applications in biological mimicking, virus inhibition, cancer therapy, and diagnosis, which contains the following two major parts: (a) pillarene-based hybrid supramolecular nanotheranostics upon hybridizing with porous materials such as mesoporous silica nanoparticles, metal-organic frameworks, metal nanoparticles, and other inorganic materials; (b) pillarene-based organic supramolecular therapeutic systems that include supramolecular amphiphilic systems, artificial channels, and prodrugs based on host-guest complexes. Finally, perspectives on how pillarene-based supramolecular nanotheranostics will advance the field of pharmaceuticals and therapeutics are given.

Polymer-based pure organic room temperature phosphorescence (RTP) materials have garnered considerable interest, among which RTP systems with prolonged lifetimes and tunable emission colors are promising for applications in sensing, flexible electronics, bioassay, anti-counterfeiting, and data encryption. Herein, facile doping method is reported based on two types of copolymers with benzene/biphenyl-based light-emitting cores as their side chains, whereby the two copolymers are robustly crosslinked via noncovalent interactions including hydrogen bonding and halogen bonding that occur between the light-emitting cores and polyacrylamide backbones. Persistent RTP emission with prolonged lifetime up to 1.9 s and phosphorescence quantum yield as high as 40.1% are obtained in single copolymers, attributed to the conformation restriction of phosphorescent dyes originating from the rigid microenvironment. Furthermore, multicolor phosphorescence signals are observed in the doped binary luminescent copolymer systems that can be effectively regulated by the feed ratio of luminescent cores and irradiation wavelengths. Possible mechanisms for this efficient and long-lived color-tunable RTP system are discussed on the basis of the experimental data and theoretical calculations. In addition, it is also demonstrated that the color-tunable RTP emission of the doped copolymer systems under ambient conditions allows for further exploitation in the application of dynamic information encryption.

We construct a fluorescent supramolecular system (TPE-Q 4 ⊂ DSP5) of excellent tolerance to a wide range of pH by the facile self-assembly of a new pillar [ 5 ] arene bearing disulfonated arms (DSP5) with an AIE-active tetraphenylethene-based tetratopic guest bearing four quaternary ammonium binding sites (TPE-Q 4 ), which exhibits strong blue emission even in dilute aqueous solutions along with much higher quantum yield and longer fluorescence lifetime than TPE-Q 4 itself. This appreciable property can be attributed to the supramolecular assembly-induced emission (SAIE) mechanism endowed by the host-guest inclusion complexation based on synthetic macrocycles. Remarkably, the enhanced fluorescence of the supramolecular assembly is quenched efficiently and exclusively by ferric ions in water with a high Stern–Volmer formula constant of 1.3 × 10 5 m o l - 1 , demonstrating the excellent cation selectivity and visualized responsiveness in ion sensing and detection.

The design and synthesis of new synthetic macrocycles has driven the rapid development of supramolecular chemistry and materials. Pillar[n]arenes, as a new type of macrocyclic compounds, are used as a promising type of building blocks for switchable supramolecular systems due to their versatile functionalization and the ability of binding toward various guest molecules. A number of guests can form inclusion complexes with pillar[n]arenes and their derivatives in solution, which are sensitive to different external triggers. Interestingly, the pursuit of complex stimuli-responsive functional materials and devices has largely motivated the shift of pillar[n]arene-based switches from solution media to surfaces for controllable macroscopic motions on solid platforms. Facilitated by the facile modification of pillar[n]arenes on various solid supports and the dynamic binding of host-guest complexes, numerous functional hybrid materials with adjustable physical or chemical properties and integrated functionalities have been reported in the last decade. Here, the advance of supramolecular switches in solution and on surfaces based on pillar[n]arenes and derivatives with an emphasis on the efforts and the latest contributions from the field is discussed.

The fabrication of smart materials is gradually becoming a research focus in nanotechnology and materials science. An important criterion of smart materials is the capacity of stimuli-responsiveness, while another lies in selective recognition. Accordingly, supramolecular host-guest chemistry has proven a promising support for building intelligent, responsive systems; hence, synthetic macrocyclic hosts, such as calixarenes, cucurbiturils, cyclodextrins, and pillararenes, have been used as ideal building blocks. Meanwhile, manipulating and harnessing light artificially is always an intensive attempt for scientists in order to meet the urgent demands of technological developments. Fluorescence resonance energy transfer (FRET), known as a well-studied luminescent activity and also a powerful tool in spectroscopic area, has been investigated from various facets, of which the application range has been broadly expanded. In this review, the innovative collaboration between FRET and supramolecular macrocyclic chemistry will be presented and depicted with typical examples. Facilitated by the dynamic features of supramolecular macrocyclic motifs, a large variety of FRET systems have been designed and organized, resulting in promising optical materials with potential for applications in protein assembly, enzyme assays, diagnosis, drug delivery monitoring, sensing, photosynthesis mimicking and chemical encryption.

Supramolecular nanovalves are an emerging class of important elements that are functionalized on the surfaces of inorganic or hybrid nanocarriers in the constructions of smart cargo delivery systems. Taking advantage of the pseudorotaxane structure via host-guest complexation and the dynamic nature of supramolecular interactions, macrocyclic arene-based supramolecular nanovalves have shown great promise in the applications of drug delivery and controlled release. Careful selection of diverse external stimuli, such as pH variations, temperature changes, redox, enzymes, light irradiation, and competitive binding, can activate the opening and closing of the nanovalves by altering the supramolecular structure or binding affinities. Meanwhile, the porous solid supports in controlled release systems also play an important role in the functionalities of the nanocarriers, which include, but not limited to, mesoporous silica nanoparticles (MSNs), metal-organic frameworks (MOFs), core-shell nanomaterials, and rare-earth porous nanomaterials. The elaborate decoration by macrocyclic arenes-based supramolecular nanovalves on porous nanomaterials has provided intelligent controlled release platforms. In this review, we will focus on the overview of supramolecular nanovalves based on two typical macrocyclic arenes, that is, calixarenes and pillarenes, and their operation manners in the controlled release processes.