Self-Assembled Nanohelixes Driven by Host-Guest Interactions and Metal Coordination.

Helical nanostructures fabricated via the self-assembly of artificial motifs have been a captivating subject because of their structural aesthetics and multiple functionalities. Herein, we report the facile construction of a self-assembled nanohelix (NH) by leveraging an achiral aggregation-induced emission (AIE) luminogen (G) and pillar[5]arene (H), driven by host-guest interactions and metal coordination. Inspired by the "sergeants and soldiers" effect and "majority rule" principle, the host-guest complexation between G and H is employed to fixate the twisted conformation of G for the generation of "contortion sites", which further induced the emergence of helicity as the 1D assemblies are formed via Ag(I) coordination and hexagonally packed into nano-sized fibers.

Smart organic materials based on macrocycle hosts.

Innovative design of smart organic materials is of great importance for the advancement of modern technology. Macrocycle hosts, possessing cyclic skeletons, intrinsic cavities, and specific guest binding properties, have demonstrated pronounced potential for the elaborate fabrication of a variety of functional organic materials with smart stimuli-responsive characteristics. In this tutorial review, we outline the current development of smart organic materials based on macrocycle hosts as key building blocks, focusing on the design principles and functional mechanisms of the tailored systems.

The Creation of DNA Origami-Based Supramolecular Nanostructures for Cancer Therapy.

DNA origami technology, a unique type of DNA nanotechnology, has attracted much attention from researchers and is applied in various fields. Through exquisite design and precise self-assembly of four kinds of deoxyribonucleotides, DNA origami nanostructures are endowed with excellent programmability and addressability and show outstanding biocompatibility in bio-related applications, especially in cancer treatment. In this review, nanomaterials based on DNA origami for cancer therapy are concluded, whereby chemotherapy and photo-assisted therapy are the main focus.

Macrocycle-Strutted Coordination Microparticles for Fluorescence-Monitored Photosensitization and Substrate-Selective Photocatalytic Degradation.

The prosperous advancement of supramolecular chemistry has motivated us to construct supramolecular hybrid materials with integrated functionalities. Herein, we report an innovative type of macrocycle-strutted coordination microparticle (MSCM) using pillararenes as the struts and "pockets", which performs unique activities of fluorescence-monitored photosensitization and substrate-selective photocatalytic degradation. Prepared via a convenient one-step solvothermal method, MSCM showcases the incorporation of supramolecular hybridization and macrocycles, endowed with well-ordered spherical architectures, superior photophysical properties, and photosensitizing capacity, where a self-reporting fluorescence response is exhibited upon photoinduced generation of multiple reactive oxygen species.

Tunable Photochromism of Spirooxazine in the Solid State: A New Design Strategy Based on the Hypochromic Effect.

As an important organic photofunctional material, spirooxazine (SO) usually does not exhibit photochromism in the solid state since the intermolecular π-π stacking impedes photoisomerization. Developing photochromic SO in the solid state is crucial for practical applications but is still full of challenges. Here, a series of spirooxazine derivatives (SO1-SO4) with bulky aromatic substituents at the 4- and 7-positions of the skeleton, which provide them with a large volume with which to undergo solid-state photochromism under mild conditions, is designed and synthesized.

Supramolecular materials based on AIEgens for photo-assisted therapy.

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.

Pillararene-based molecular-scale porous materials.

This review discusses the design and syntheses of molecular-scale pillar[]arene-based porous materials with promising applications and summarises the development of using pillar[]arenes as the building blocks of porous materials. From the perspective of "role of participation" in the syntheses of molecular-scale pillar[]arene-based porous materials, the content can be divided into pillar[]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.

A stimuli-responsive pillar[5]arene-based hybrid material with enhanced tunable multicolor luminescence and ion-sensing ability.

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 Fe.

Polyacrylamide-Based Binary Luminescent Copolymer Materials Exhibit Color-Tunable and Efficient Long-Lived Room Temperature Phosphorescence.

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.

Pyridine-Conjugated Pillar[5]arene: From Molecular Crystals of Blue Luminescence to Red-Emissive Coordination Nanocrystals.

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.

Supramolecular Nanoplatform Based on Mesoporous Silica Nanocarriers and Pillararene Nanogates for Fungus Control.

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.

Recent Advances of Polymer-Based Pure Organic Room Temperature Phosphorescent Materials.

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.

Supramolecular Engineering of Efficient Artificial Light-Harvesting Systems from Cyanovinylene Chromophores and Pillar[5]arene-Based Polymer Hosts.

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).

Pillar[n]arene-Based Supramolecular Switches in Solution and on Surfaces.

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.

Supramolecular nanomaterials based on hollow mesoporous drug carriers and macrocycle-capped CuS nanogates for synergistic chemo-photothermal therapy.

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. : 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. : 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.

A Binary Supramolecular Assembly with Intense Fluorescence Emission, High pH Stability, and Cation Selectivity: Supramolecular Assembly-Induced Emission Materials.

We construct a fluorescent supramolecular system (TPE-Q 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), which exhibits strong blue emission even in dilute aqueous solutions along with much higher quantum yield and longer fluorescence lifetime than TPE-Q 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.

Enhanced Solution and Solid-State Emission and Tunable White-Light Emission Harvested by Supramolecular Approaches.

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.

Supramolecular nanotheranostics based on pillarenes.

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.

Gated Materials: Installing Macrocyclic Arenes-Based Supramolecular Nanovalves on Porous Nanomaterials for Controlled Cargo Release.

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.

Pillararene-Based Fluorescent Supramolecular Systems: The Key Role of Chain Length in Gelation.

Four supramolecular assemblies are fabricated from two pillararene tetramers with aggregation-induced emission properties (SH and LH) and two different lengths of neutral guests with three binding sites (arms) for pillararene cavities (SG and LG) through host-guest interactions, and their fluorescent behaviors in organic solvent are investigated. SG⊂SH exhibits the largest fluorescent enhancement in chloroform due to supramolecular assembly-induced emission enhancement, while only LG⊂LH turns into supramolecular gel with stimuli responsiveness owing to their most flexible arms.

Fluorescence Resonance Energy Transfer Systems in Supramolecular Macrocyclic Chemistry.

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.