The development of π‐conjugated molecular systems with high‐efficiency generation of UV and blue light plays an important role in the fields of light‐emitting diodes, fluorescent imaging, and information storage. Herein, supramolecular construction of solid‐state UV/blue luminescent materials are assembled using 2,5‐diphenyloxazole (DPO) with four typical co‐assembled building blocks (1,4‐diiodotetrafluorobenzene, 4‐bromotetrafluorobenzene carboxylic acid, pentafluorophenol, and octafluoronaphthalene). Compared with the pristine DPO sample, the as‐prepared two‐component molecular materials feature ease of crystallization, high crystallinity, enhanced thermal stability and tunable luminescence properties (such as emissive wavelength, color, fluorescence lifetime, and photoluminescence quantum yield) as well as multicolor polarized emission in the UV/blue region. Moreover, pump‐enhanced luminescence and reversible mechanochromic fluorescence (MCF) properties can also be obtained for these molecular solids, which are absent for the pristine DPO sample. Therefore, this work provides a procedure for the facile self‐assembly of ordered two‐component molecular materials with tunable UV/blue luminescence properties, which have potential application in the areas of light‐emitting displays, polarized emission, frequency doubling, and luminescent sensors.

Co-assembly of chromophore guests with host matrices can afford materials which have photofunctionalities different from those of individual components. Compared with clay and zeolite materials, the use of metal–organic frameworks (MOFs) as a host structure for fabricating luminescent host–guest materials is still at an early stage. Herein, we report the incorporation of a laser dye, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), into stilbene-based and naphthalene-based MOF systems. The resulting materials exhibit blue/red two-color emission, and the intensity ratio of blue to red fluorescence varies in different planes within the MOF crystal as detected by 3D confocal fluorescence microscopy. The observed changes in ratiometric fluorescence suggest the occurrence of energy transfer from MOF host to DCM molecules, which can be further confirmed by periodic density functional theoretical (DFT) calculations. Moreover, selective changes in luminescence behavior are observed on treating the guest@MOF samples with volatile organic compounds (methanol, acetone and toluene), indicating that these host–guest systems have potential applications as fluorescence sensors. It can be expected that by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels, a wide variety of multi-color luminescent and energy-transfer systems can readily be prepared in a similar manner.

Stimuli-responsive luminescent materials play an important role in fluorescent switches, optical storage devices and smart sensors. In this work, we report a mechano-induced and solvent stimuli-responsive luminescent change by the assembly of a typical aggregation-induced-emissive (AIE) molecule, niflumic acid (NFC), into the interlayer region of Zn–Al-layered double hydroxides (LDHs) with heptanesulfonate (HPS) as a cointercalation guest. The structure, chemical composition, and thermostability of the as-prepared NFC-HPS/LDHs composites were characterized by X-ray diffraction, elemental analysis, and thermogravimetry and differential thermal analysis (TG-DTA). Fluorescence spectra demonstrate that the sample with 5% NFC initial molar percentage, with respect to the interlayer guests, exhibits the optimal luminescent intensity. The NFC-HPS/LDH (5%) sample also exhibits the most obvious luminescent mechano-response with a 16 nm blue-shift and increase in the fluorescent intensity after grinding, while the pristine NFC solid shows little to no mechano-responsive behavior. Moreover, the NFC-HPS/LDH (5%) also presents reversible luminescent response to different volatile organic compounds (VOCs) (such as tetrahydrofuran, methanol, acetone, toluene, and chloroform). Therefore, this work not only gives a detailed description on the dual stimuli (mechanics and solvent)-responsive luminescence for future sensor applications but also supplies a deep understanding of the optical properties of the new AIE molecule within the confined LDH layers.

The formation of two-component molecular cocrystals can lead to the tunable excited state intramolecular proton transfer (ESIPT) process and emission, as first confirmed by both experimental and computational studies.

Based on a supramolecular assembly strategy, Yan and co‐workers obtain two‐component molecular solid‐state materials of diphenyloxazole (DPO) through a solution‐growth process. On page 587, the DPO‐based high‐quality single crystals display tunable luminescence properties (such as emissive wavelength, color, and fluorescence lifetime) as well as multicolor polarized emission in the UV/blue/green region. This is similar to, in a macroscopic scenario, the variable light emitted from Canton tower (the highest tower in China, shown here) at the side of the Zhujiang river.

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