Nearly Unity Quantum Yield Persistent Room-Temperature Phosphorescence from Heavy Atom-Free Rigid Inorganic/Organic Hybrid Frameworks.

Synergism between covalent and non-covalent bonds is employed to fix an organic phosphor guest in a rigid inorganic framework, simulating the stiffening effect seen in the glassy state and realizing efficient and ultralong room-temperature phosphorescence (RTP). Twelve heavy-atom-free composites have been obtained through introducing arylboric or arylcarboxylic acid derivatives into the inorganic boric acid matrix by solid-phase synthesis. Owing to the stiffening effect of multiple bonds, all the composites show highly efficient and persistent RTP of guest molecules with a quantum yield ranging from 39.8 % to ca. 100 % and a lifetime up to 8.74 s, which results in a 55 s afterglow visible to the naked eye after exposure to a portable UV lamp. Interestingly, it is found that the substitution position and quantity of carboxyl in the guest have a great influence on the phosphorescent properties, and that the heavy-atom effect is invalid in such host-guest hybrid systems. The 100 g grade composite is easily prepared because of the solvent-free, green, and simple synthesis method. These results provide an important way for the development of RTP materials with ultrahigh quantum yield and ultralong lifetime, as well as their practical applications in the fields of anti-counterfeiting and information storage, among others.

Photoinduced π-Bond breakage causing dynamic closing-opening shell transition of Z-type Diphenylmaleonitriles molecules.

Organic molecules with dynamic covalent-bonding characteristics have attracted much attention for their important role in constructing stimulus-responsive smart materials. However, it is difficult to realize sensitive and reversible covalent bond cleavage/formation through external stimuli in the aggregated state of molecules. Herein, a series of 2,3-diphenylmaleonitriles (DPMNs) with photoinduced π-bond cleavage properties have been designed and synthesized to construct the dynamic covalent bond materials. The cis-form 2,3-diphenylmaleonitriles (Z-DPMNs) exhibit significant photochromism in both solid and solution states under ultraviolet light and visible light. The photochromism stems from the photoinduced π-bond splitting of Z-DPMNs, resulting in a transition from the closed-shell to open-shell structure. Moreover, the twisted structure and molecular stacking of Z-DPMNs, the push-pull electron effect of substituents, and the external factors including temperature and solvent polarity have important effects on the dynamic conversion of π-bonds. Based on the sensitive and reversible optical performance transformation, Z-DPMNs can be applied as safety ink in anti-counterfeiting, information encryption and storage systems. This work not only provides an approach for constructing dynamic covalent bonds but also greatly enriches stimulus-responsive materials.

Full-color Persistent Room-temperature Phosphorescence from Carbon Dot Composites Based on a Single Nonaromatic Carbon Source.

Herein, a series of carbon dot composites (CDC) with full-color and long-lived room-temperature phosphorescence (RTP) are prepared by a simple solid-phase one-step method from a single non-conjugated and non-aromatic carbon source. The RTP emission wavelength can be adjusted from 462 to 623 nm by changing the feeding ratio and reaction temperature. The luminescent lifetime and quantum yield of a green emissive CDC (AB-CDC-3) reach 1.1 s and 39%, respectively, because of the close interaction between carbon dots and inorganic matrix. Due to the existence of multiple luminescent centers, these CDC exhibit excitation wavelength-dependent RTP and a white emission when excited at a specific wavelength. A single-component afterglow luminescent diode based on AB-CDC-4 shows a high-quality white emission with CIE of (0.30, 0.33) and color-rendering index of 88. Based on the unique photophysical properties of the composites, they exhibit huge application potential in the field of multilevel anti-counterfeiting, fingerprint identification, and optoelectronic devices.