Multiple Light Source-Excited Organic Manganese Halides for Water-Jet Rewritable Luminescent Paper and Anti-Counterfeiting

Abstract

Rewritable luminescent paper is particularly crucial, considering the ultrahigh paper consumption and confidential information security, but a highly desirable stimuli-responsive smart luminescent material with excellent water solubility has rarely been studied. Herein, a new type of rewritable paper made by highly efficient green light emissive zero-dimensional (0D) organic manganese halides is rationally designed by virtue of the reversible photoluminescence (PL) off−on switching. Specifically, the green emission can be linearly quenched by water vapor in a wide humidity range and again recovered in a dry atmosphere, which make it a smart hydrochromic PL off−on switching and humidity sensor. Benefiting from the reversible luminescence off−on switch and excellent water solubility, rewritable luminescent paper is realized through waterjet security printing technology on 0D halide-coated commercial paper with high resolution. The printed/written information can be easily cleaned by slight heating with outstanding "write−erase−write" cycle capabilities. In addition, multiple light source-induced coincident green light emissions further provide convenience to realize anti-counterfeiting, encryption and decryption of confidential information, and so forth. This work highlights the superiority of dynamic ionic-bonded 0D organic manganese halides as reversible PL switching materials in rewritable luminescent paper, high-security-level information printing, storage and protection technologies, and so forth.

Two Organic–Inorganic Manganese(II) Halide Hybrids Showing Compelling Photo- and Mechanoluminescence as well as Rewritable Anticounterfeiting Printing

“…This is likely ascribed to the TPA organic cation in 2 having a longer carbon chain and more C–H bonds than TEA ligands in 1 . The longer carbon chain and more C–H bonds induce higher vibrations to promote nonradiative transitions, which lead to the decrease of the radiative transitions and quantum yield …”

“…The longer carbon chain and more C−H bonds induce higher vibrations to promote nonradiative transitions, which lead to the decrease of the radiative transitions and quantum yield. 45 The high thermal stability and quantum yield of 1 and 2 make them excellent emitters for light-emitting devices (LEDs). Generally, to meet the requirement of practical applications, the emitters need to maintain good photostability in the temperature range of 363−383 K. 66 In order to further study the photostability of 1 and 2, the high-temperature emission spectra were recorded below the phase transition temperature (see the "Thermal Properties section").…”

“…Interestingly, rewritable and multilevel security printing was achieved by using water as ink to break the ionic bonds of OIMHs by Zhao’s group . Lei reported a family of OIMHs with reversible off–on switching luminescence, which can be used in water-jet rewritable printing, anticounterfeiting, and encryption and decryption . Although significant progress has been made, − rewritable anticounterfeiting printing based on OIMHs as an emitter is still in its infancy and deserves to be thoroughly explored.…”

“…44 Lei reported a family of OIMHs with reversible off−on switching luminescence, which can be used in water-jet rewritable printing, anticounterfeiting, and encryption and decryption. 45 Although significant progress has been made, 44−48 rewritable anticounterfeiting printing based on OIMHs as an emitter is still in its infancy and deserves to be thoroughly explored. Taking all of the above into account, two OIMHs with formulas of [(TEA)(TMA)]MnCl 4 (1) and [(TPA)(TMA) 3 ]-(MnCl 4 ) 2 (2) (TEA = tetraethylammonium, TMA = tetramethylammonium, and TPA = tetrapropylammonium) were synthesized by a mixed-ligand strategy and their structures were determined by single crystal X-ray diffraction.…”

Water-stable, biocompatible, and highly luminescent perovskite nanocrystals-embedded fiber-based paper for anti-counterfeiting applications

“…Furthermore, paper based on luminescent materials is also becoming as a promising candidate for anti-counterfeiting application. Consequently, significant efforts have been devoted in the development of luminescent paper for anti-counterfeiting applications in recent time which reveals that these paper could be an excellent applicant for anti-counterfeiting application [ 27 – 29 ]. In most of these efforts, luminescent paper based on organic compounds and dyes have many drawbacks such as photostability, low PLQY, high cost, complex and multistep synthesis route, low water-solubility [ 27 , 28 , 30 – 35 ].…”