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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.

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.

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.

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.

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.