Crystallization‐Induced Emission Enhancement of a Deep‐Blue Luminescence Material with Tunable Mechano‐ and Thermochromism

Organic luminescent materials with the ability to reversibly switch the luminescence when subjected to external stimuli have attracted considerable interest in recent years. However, the examples of luminescent materials that exhibit multiresponsive properties are rarely reported. In this work, a new stimuli‐responsive dye P1 is designed and synthesized with two identical chromophores of naphthalimide, one at each side of an amidoamine‐based spacer. This amide‐rich molecule offers many possibilities for forming intra‐ and intermolecular hydrogen bond interactions. Particularly, P1 has an intrinsic property of cocrystallizing with methanol. Compared with the pristine P1 sample, the as‐prepared two‐component cocrystalline material displays an exceptive deep‐blue emission, which is extremely rare among naphthalimide‐based molecules in the solid state. Furthermore, the target material exhibits an obvious mechanochromic fluorescent behavior and a large spectral shift under force stimuli. On the other hand, the cocrystalline material shows an unusual “turn off” thermochromic luminescence accompanied by solvent evaporation. Moreover, using external stimuli to reversibly manipulate fluorescent quantum yields is rarely reported to date. The results demonstrate the feasibility of a new design strategy for solid‐state luminescence switching materials: the incorporation of solvents into organic compounds by cocrystallization to obtain a crystalline state luminescence system.     

A Colorimetric Hydrocarbon Sensor Employing a Swelling‐Induced Mechanochromic Polydiacetylene

Exceptional challenges have confronted the rational design of colorimetric sensors for saturated aliphatic hydrocarbons (SAHCs). The main reasons for this difficulty are the extremely nonpolar nature of these targets and their lack of functional groups that can interact with probes. By taking advantage of a mechanochromic conjugated polydiacetylene (PDA) and the hydrocarbon‐induced swelling properties of polydimethylsiloxane (PDMS), a sensor film that enables simple, colorimetric differentiation between a variety of C5 to C14 aliphatic hydrocarbons is fabricated. The unprecedented PDA–PDMS composite sensor undergoes a blue‐to‐red colorimetric transition on a timescale that is dependent on the chain length of the hydrocarbon target. In addition, the development of the red color is directly proportional to the swelling ratio of the film. This straightforward approach enables naked‐eye differentiation between n‐pentane and n‐heptane. The versatility of the sensor system is demonstrated by using it for the colorimetric determination of kerosene in adulterated diesel oil. Finally, the observation that a PDA microcrystal in the film undergoes significant expansion and tearing in concert with a blue‐to‐red colorimetric transition during the swelling process provides direct evidence for the mechanism for the mechanochromic behavior of the PDA.     

Photonic Vitrimer Elastomer with Self-Healing,High Toughness,Mechanochromism, and Excellent Durability based on Dynamic Covalent Bond

Vitrimers, with their unique dynamic covalent bonds, possess attractive self-healability and mechanical robustness, providing an intriguing opportunity to construct functional soft materials. However, their potential for function recovery, especially optical function, is underexplored. Harnessing the synergistic effect of photonic crystals and vitrimers, a novel photonic vitrimer with light regulating and self-healing capabilities is presented. The resulting photonic vitrimer exhibits a large tensile strain (>1000%), high toughness (21.2 kJ m⁻³), bright structural color, and mechanochromism. Notably, the structural color remains constant even after 10 000 stretching/releasing cycles, showing superior mechanical stability, creep-resistance, and excellent durability. More importantly, the exchange of dynamic covalent bonds imparts the photonic vitrimer with a self-healing ability (>95% efficiency), enabling the recovery of its optical function. Benefiting from the above merits, the photonic vitrimer has been successfully used as a sensor for human motion detection, which demonstrates visualized interactive sensibility even after self-repairing. This material design provides a general strategy for optical functionalization of vitrimers. The photonic vitrimer elastomers present great potential as resilient functional soft materials for diverse flexible devices and a novel optical platform for soft robotics, smart wearable devices, and human-machine interaction.     

Cephalopod‐Inspired High Dynamic Range Mechano‐Imaging in Polymeric Materials

Cephalopods, such as squid, cuttlefish, and octopuses, use an array of responsive absorptive and photonic dermal structures to achieve rapid and reversible color changes for spectacular camouflage and signaling displays. Challenges remain in designing synthetic soft materials with similar multiple and dynamic responsivity for the development of optical sensors for the sensitive detection of mechanical stresses and strains. Here, a high dynamic range mechano‐imaging (HDR‐MI) polymeric material integrating physical and chemical mechanochromism is designed providing a continuous optical read‐out of strain upon mechanical deformation. By combining a colloidal photonic array with a mechanically responsive dye, the material architecture significantly improves the mechanochromic sensitivity, which is moreover readily tuned, and expands the range of detectable strains and stresses at both microscopic and nanoscopic length scales. This multi‐functional material is highlighted by creating detailed HDR mechanographs of membrane deformation and around defects using a low‐cost hyperspectral camera, which is found to be in excellent agreement with the results of finite element simulations. This multi‐scale approach to mechano‐sensing and ‐imaging provides a platform to develop mechanochromic composites with high sensitivity and high dynamic mechanical range.     

Reversible Crystal-to-Crystal Phase Transitions with High-Contrast Luminescent Alterations for a Thermally Activated Delayed Fluorescence Emitter

Merging thermally activated delayed fluorescence (TADF) and mechanochromic luminescence (MCL) into one single molecule is a promising strategy for developing multifunctional organic materials. Herein, a unique multifunctional molecule TPA-DQP, comprising a large π-conjugated diquinoxalino[2,3-a:2′,3′-c]phenazine (DQP) as the acceptor and triphenylamine (TPA) as the donor, is designed and synthesized. TPA-DQP possesses polymorphism, efficient TADF emission as well as MCL property with high-contrast in emission colors from 576 to 706 nm. Reversible crystal-to-crystal phase transitions in response to external stimuli such as vapor fuming and heating are realized on the basis of the two polymorphs of TPA-DQP. The distinct crystal-to-crystal phase transition is attributed ultimately to the change of packing arrangements and intermolecular interactions of the two polymorphs under stimuli. Furthermore, TPA-DQP-based organic light emitting diode (OLED) device achieves external quantum efficiency as high as 18.3% at 676 nm, which represents the best performance for deep-red OLEDs based on MCL-active TADF emitters. This study reports a novel MCL-active TADF material that exhibits crystal-to-crystal phase transition and brings insight into the underlying relationship between molecular packing modes and the photoluminescent behavior.     

Mechano‐ and Photochromism from Bulk to Nanoscale: Data Storage on Individual Self‐Assembled Ribbons

A Pt(II) complex, bearing an oligo‐ethyleneoxide pendant, is able to self‐assemble in ultralong ribbons that display mechanochromism upon nanoscale mechanical stimuli, delivered through atomic force microscopy (AFM). Such observation paves the way to fine understanding and manipulation of the mechanochromic properties of such material at the nanoscale. AFM allows quantitative assessment of nanoscale mechanochromism as arising from static pressure (piezochromism) and from shear‐based mechanical stimuli (tribochromism), and to compare them with bulk pressure‐dependent luminescence observed with diamond‐anvil cell (DAC) technique. Confocal spectral imaging reveals that mechanochromism only takes place within short distance from the localized mechanical stimulation, which allows to design high‐density information writing with AFM nanolithography applied on individual self‐assembled ribbons. Each ribbon hence serves as an individual microsystem for data storage. The orange luminescence of written information displays high contrast compared to cyan native luminescence; moreover, it can be selectively excited with visible light. In addition, ribbons show photochromism, i.e., the emission spectrum changes upon exposure to light, in a similar way as upon mechanical stress. Photochromism is here conveniently used to conceal and eventually erase information previously written with nanolithography by irradiation.     

Structural Coloration with Nonclose‐Packed Array of Bidisperse Colloidal Particles

Colloidal crystals and glasses have their own photonic effects. Colloidal crystals show high reflectivity at narrowband, whereas colloidal glasses show low reflectivity at broadband. To compromise the opposite optical properties, a simple means is suggested to control the colloidal arrangement between crystal and glass by employing two different sizes of silica particles with repulsive interparticle potential. Monodisperse silica particles with repulsive potential spontaneously form crystalline structure at volume fraction far below 0.74. When two different sizes of silica particles coexist, the arrangement of silica particles is significantly influenced by two parameters: size contrast and mixing ratio. When the size contrast is small, a long‐range order is partially conserved in the entire mixing ratio, resulting in a pronounced reflectance peak and brilliant structural color. When the size contrast is large, the long‐range order is rapidly reduced along with mixing ratio. Nevertheless, a short‐range order survives, which causes low reflectivity at a broad wavelength, developing faint structural colors. These findings offer an insight into controlling the colloidal arrangements and provide a simple way to tune the optical property of colloidal arrays for structural coloration.