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0D Hybrid Zn/Cd Halied for Color-Time-Dual-Resolved Security Applications: We devise a family of zero-dimensional (0D) hybrid metal halides based RTP materials with dual phosphorescence performance and adjustable lifetime scale, which realize color-lifetime-dual-resolved encoding ability, showcasing potential applications in multilevel anti-counterfeiting and information security. [Display omitted] • A new optical multiplexing concept of simultaneously utilizing the varied emission color and lifetime as dual temporary codes was proposed. • A new family of zero-dimensional (0D) organic metal halides was directly synthesized accompanied by tailorable lifetime at the same molecular platform. • High-security anti-Counterfeiting and 4D information encryption-decryption were demonstrated. Luminescent materials with engineered optical properties play an important role in anti-counterfeiting and information security technology. However, conventional luminescent coding is limited by fluorescence color or intensity, and high-level multi-dimensional luminescent encryption technology remains a critically challenging goal in different scenarios. To improve the encoding capacity, we present an optical multiplexing concept by synchronously manipulating the emission color and decay lifetimes of room-temperature phosphorescence materials at molecular level. Herein, we devise a family of zero-dimensional (0D) hybrid metal halides by combining organic phosphonium cations and metal halide tetrahedral anions as independent luminescent centers, which display blue phosphorescence and green persistent afterglow with the highest quantum yields of 39.9 % and 57.3 %, respectively. Significantly, the luminescence lifetime can be fine-tuned in the range of 0.0968–0.5046 μs and 33.46–125.61 ms as temporary time coding through precisely controlling the heavy atomic effect and inter-molecular interactions. As a consequence, synchronous blue phosphorescence and green afterglow are integrated into one 0D halide platform with adjustable emission lifetime acting as color- and time-resolved dual RTP materials, which realize the multiple applications in high-level anti-counterfeiting and information storage. The color-lifetime-dual-resolved encoding ability greatly broadens the scope of luminescent halide materials for optical multiplexing applications. [ABSTRACT FROM AUTHOR]

Despite rapid progress and wide applications of room temperature phosphorescence (RTP) materials, it is still a great challenge to optimize the RTP activity through rational structural design at a molecular level. Herein, a successful cationic engineering strategy is demonstrated to modulate the crystal flexibility achieving controllable RTP in a new pair of metal halides [APML]ZnCl4 ([APML] = N‐(3‐Aminopropyl)morpholine) and [AEML]ZnCl4 ([AEML] = N‐(2‐Aminoethyl)morpholine). Both halides display blue fluorescence under 365 nm UV. Comparing with longer [APML]+, shorter [AEML]+ significantly enhances crystal rigidity and restrains non‐radiative scattering, boosting photoluminescence quantum yield (PLQY) from 18.89% to 22.41%. Synchronously, enhanced crystal rigidity significantly promotes the inter‐system crossing from singlet to triplet excited states. As a consequence, [AEML]ZnCl4 displays long‐lived green RTP property with millisecond scale lifetime in contrast to the blank RTP activity of [APML]ZnCl4. Comprehensive investigations demonstrate that the energy transfer between inorganic and organic components greatly changes the redistribution of singlet and triplet excited states, resulting in distinct phosphorescence activity. The different short‐lived blue fluorescence and long‐lived green phosphorescence provide a color‐time‐dual‐resolved luminescent tag with advanced applications in anti‐counterfeiting, etc. This work highlights a new structural engineering strategy to achieve controllable RTP affording a guide to rationally design RTP materials. [ABSTRACT FROM AUTHOR]

In recent years, low-dimensional organic–inorganic hybrid metal halides have attracted great attention in the field of solid-state optical materials due to their outstanding luminescence properties. Here, one new zero-dimensional (0D) hybrid zinc bromide [N-EPD]2ZnBr4 (N-EPD = N-ethylpyridinium) was prepared through a conventional solvothermal reaction method. The crystal structure of [N-EPD]2ZnBr4 consists of a discrete [ZnBr4]2− tetrahedron and organic [N-EPD] cation. It is noteworthy that [N-EPD]2ZnBr4 displays strong yellow broadband luminescence with a promising photoluminescence quantum yield (PLQY) of 8.28%. Based on temperature-dependent, time-resolved spectroscopy characterization and theoretical studies, the broadband yellow emission can be attributed to radiative recombination of self-trapping excitons (STEs). To the best of our knowledge, this is the first report about yellow light emission in 0D hybrid zinc halides. [ABSTRACT FROM AUTHOR]