Hydrophilic Cocrystals with Water Switched Luminescence.

Utilizing water molecules to regulate the luminescence properties of solid materials is highly challenging. Herein, we develop a strategy to produce water-triggered luminescence-switching cocrystals by coassembling hydrophilic donors with electron-deficient acceptors, where 1,2,4,5-Tetracyanobenzene (TCNB) was used as the electron acceptor and pyridyl benzimidazole derivatives were used as the electron donors enabling multiple hydrogen-bonds. Two cocrystals, namely 2PYTC and 4PYTC were obtained and showed heat-activated emission, and such emission could be quenched or weakened by adding water molecules. The cocrystal structure exhibited the donor molecule that can form multiple hydro bonds with water and acceptor molecules due to the many nitrogen atoms of them. The analyses of the photophysical data, powder X-ray diffraction, and other data confirmed the reversible fluorescence "on-off" effects were caused by eliminating and adding water molecules in the crystal lattice. The density functional theory calculations indicate that the vibration of the O-H bond of water molecules in the cocrystal can absorb the excitation energy and suppress fluorescence. Furthermore, the obtained cocrystals also showed temperature, humidity, and H+ /NH4 + responsive emission behavior, which allows their applications as thermal and humidity sensors, and multiple information encryptions. This research paves the way for preparing intelligent hydrophilic organic cocrystal luminescent materials.

Reversible Luminescent Switching Induced by Heat/Water Treatment in a Zero-Dimensional Hybrid Antimony(â ¢) Chloride.

Recently zero-dimensional (0-D) inorganic-organic metal halides (IOMHs) have become a promising class of optoelectronic materials. Herein, we report a new photoluminescent (PL) 0-D antimony(III)-based IOMH single crystal, namely [H2BPZ][SbCl5]·H2O (BPZ = benzylpiperazine). Photophysical characterizations indicate that [H2BPZ][SbCl5]·H2O exhibits singlet/triplet dual-band emission. Density functional theory (DFT) calculations suggest that [H2BPZ][SbCl5]·H2O has the large energy difference between singlet and triplet states, which might induce the dual emission in this compound. Temperature-dependent PL spectra analyses suggest the soft lattice and strong electron-phonon coupling in this compound. Thermogravimetric analysis shows that the water molecules in the lattice of the title crystal could be removed by thermal treatment, giving rise to a dehydrated phase of [H2BPZ][SbCl5]. Interestingly, such structural transformation is accompanied by a reversible PL emission transition between red light (630 nm, dehydrated phase) and yellow light (595 nm, water-containing phase). When being exposed to an environment with 77% relative humidity, the emission color of the dehydrated phase was able to change from red to yellow within 20 s, and the red emission could be restored after reheating. The red to yellow emission switching could be achieved in acetone with water concentration as low as 0.2 vol%. The reversible PL transition phenomenon makes [H2BPZ][SbCl5]·H2O a potential material for luminescent water-sensing.

Reversible Luminescent Switching in an Organic Cocrystal: Multi-Stimuli-Induced Crystal-to-Crystal Phase Transformation.

A luminescent cocrystal system is reported to undergo crystal-to-crystal phase transformation from yellow-emitting polymorph I to green-emitting polymorph II, triggered by THF fuming or heating, and the green emission can recover to the initial yellow emission by grinding. The established spectroscopic and crystallographic analyses demonstrate that the phase transition occurred and benefits from the combined effect of similar molecular arrange sequence and unique alteration of intermolecular interactions from halogen/hydrogen bonds in I to π-π stacking in II. Furthermore, I and II exhibit red-shift emission under hydrostatic pressure. The emission of I and II shows a red-shift and recovers towards the initial emission upon acid-base fuming. This is a rare example of reversible luminescent switching of cocrystal based upon crystal-to-crystal phase transition, and provides an alternative strategy to develop multi-stimuli responsive materials.

Lanthanide-Polyoxometalate-Based Film with Reversible Photochromism and Luminescent Switching Properties for Erasable Inkless Security Printing.

Security printing is of the utmost importance in the information era. However, the excessive use of inks and paper still faces many economic and environmental issues. Thus, developing erasable inkless security printing materials is a remarkable strategy to save resources, protect the environment, and improve information security. To this endeavor, a photoresponsive lanthanide-polyoxometalate-doped gelatin film with high transparency was developed through the solution casting method. Attenuated total reflection Fourier-transform infrared spectroscopy confirmed the electrostatic and hydrogen bond interactions between gelatin and lanthanide-polyoxometalate. Absorption spectra, luminescent spectra, and digital images indicated that the film displayed reversible photochromism behavior and was accompanied by luminescent switching property upon exposure to UV irradiation and oxygen (in the dark) alternately, which allowed its potential application as a reprintable medium for inkless security printing. The printed information can be erased upon exposure to oxygen in the dark, and the film can be reused for printing again. The film exhibited excellent erasability, reprintability, renewability, and low toxicity. In addition, multiple encryption strategies were designed to improve information security. This work offers an attractive alternative strategy for constructing a reprintable film for inkless security printing in terms of simplifying the preparation process, saving resources, and protecting the environment.

Lanthanide Polyoxometalate Based Water-Jet Film with Reversible Luminescent Switching for Rewritable Security Printing.

Luminescent security printing is of particular importance in the information era. However, the use of conventional paper still carries a lot of economic and environmental issues. Therefore, developing new environmentally friendly security printing material with a low cost is imperative. To achieve the aforementioned goals, novel lanthanide polyoxometalate doped gelatin/glycerol films with high transparency, high strength, and good flexibility have been developed via a solution-casting method. The electrostatic interaction between zwitterionic gelatin and polyoxometalate was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. Luminescent spectra and digital images indicated that the films exhibited reversible luminescent switching properties through association and dissociation of hydrogen bonds between glycerol and water molecules, allowing its potential application as water-jet rewritable paper for luminescent security printing. Furthermore, the printed information can be conveniently "erased" by heating, and the film can be reused for printing. The film exhibited excellent ability to be both rewritten and re-erased. A QR code pattern and hybrid printing were employed to improve the security of information. In addition, the rewritable films possessed excellent regeneration ability and low toxicity, as well as good stability against UV irradiation and organic solvents. The water-jet rewritable film based on lanthanide polyoxometalate for luminescent security printing, to the best of our knowledge, has not yet been reported up to date. This work provides an attractive alternative strategy on fabricating rewritable films for luminescent security printing in terms of cutting down the cost, simplifying the preparation process, and protecting the environment.

Self-Healing Material with Reversible Luminescence Switch Behavior.

Luminescent materials with dynamic responsiveness to external stimuli have attracted extensive attention for the development of advanced sensors and smart materials; however, self-healing capability is also of great importance for functional soft materials. An acid/base vapor reversibly triggered luminescence switch with self-healing ability is achieved by incorporating dynamic lanthanide metal-ligand (Ln-L) coordination into the soft polydimethylsiloxane polymer network. The emission color of the resultant luminescent material could be modulated by altering either the Eu3+/Tb3+ molar ratio or the excitation wavelength. The luminescence "On-Off" reversible switch is realized via direct alternating exposure to acid and base vapor, realizing reversible information encryption and decryption. The dynamic Ln-L cross-link as well as the hydrogen bond in the luminescent material endow it with excellent self-healing capability, high toughness, and stretchability. We believe this acid/base vapor-triggered self-healing switching strategy provides new insights for expanding the application range of luminescent materials.

Tunable Luminescence Contrast of Na0.5Bi4.5Ti4O15:Re (Re = Sm, Pr, Er) Photochromics by Controlling the Excitation Energy of Luminescent Centers.

High luminescent switching contrast of photochromic materials is extremely important in improving the sensitivity and resolution of optical switches and high-density optical data storage devices. To date, conventional methods, such as tuning absorption and emission bands based on electron or resonance energy transfer mechanisms in well-known organic photochromic molecules or compounds, have routinely been adopted to tune luminescent switching behavior. However, these strategies and mechanisms are not effectively applied to luminescence switching in inorganic materials because their crystal structures differ strongly from those of organic materials. In this paper, we report a new method to significantly tune the luminescent switching contrast by modifying the excitation energy of luminescent centers in a newly synthesized photochromism material: Na0.5Bi4.5Ti4O15:Re (Re = Sm, Pr, Er). A significant enhancement of luminescence switching contrast was achieved when the luminescent centers were excited by low energy photons at a given irradiation wavelength, intensity, and time, compared with high excitation energy photons. The trend "the lower the excitation energy, the higher the luminescence switching contrast" is universal in different rare earth ion-doped Na0.5Bi4.5Ti4O15 ferroelectrics. The changes in the luminescent switching contrast based on excitation energy are ascribed to nonradiative energy transfer from the luminescent center to the color center by dipole-dipole interactions according to Dexter theory. This possible utilization of excitation energy at lower energy levels is usually less destructive to both information recording and the recording material itself during luminescent readout processes while achieving higher luminescence switching contrast.

Controlled growth, intense upconversion emissions and concentration induced luminescence switching of bifunctional Tm(3+) doped hexagonal NaYb0.55Gd0.45F4 nanorods.

Bifunctional hexagonal Tm(3+) doped NaYb0.55Gd0.45F4 nanorods with tunable size are prepared via in situ cation-exchange reaction using hydrothermal method. The measured field dependence of magnetization of the NaYb0.55Gd0.45F4 nanorods shows typical paramagnetic characteristics that can be ascribed to the non-interacting localized nature of the magnetic moment of rare-earth ions. When excited by a 980nm laser, these nanorods exhibit intense multi-color up-conversion (UC) emissions in infrared, red, blue and especially ultraviolet. In addition, luminescent switching between different UC emission wavelengths of 480nm and 450nm is observed by adjusting Tm(3+) doping concentration. Based on power-dependent spectral analyses, it is found that with the increase of Tm(3+) doping concentration, due to the suppressed saturation effect, the dominative UC process redistribute the populations at (1)G4 and (1)D2(Tm(3+)) states of Tm(3+) ion resulting in the above luminescent switching. Our results indicate that bifunctional hexagonal NaYb1-xGdxF4 nanocrystals have potential applications in miniaturized solid-state light sources, optical processing sensors and fluorescent biolabels.