Zero-dimensional halide hybrid bulk glass exhibiting reversible photochromic ultralong phosphorescence.

Dynamically responsive materials, capable of reversible changes in color appearance and/or photoemission upon external stimuli, have attracted substantial attention across various fields. This study presents an effective approach wherein switchable modulation of photochromism and ultralong phosphorescence can be achieved simultaneously in a zero-dimensional organic-inorganic halide hybrid glass doped with 4,4´-bipyridine. The facile fabrication of large-scale glasses is accomplished through a combined grinding-melting-quenching process. The persistent luminescence can be regulated through the photochromic switch induced by photo-generated radicals. Furthermore, the incorporation of the aggregation-induced chirality effect generates intriguing circularly polarized luminescence, with an optical dissymmetry factor (glum) reaching the order of 10-2. Exploiting the dynamic ultralong phosphorescence, this work further achieves promising applications, such as three-dimensional optical storage, rewritable photo-patterning, and multi-mode anti-counterfeiting with ease. Therefore, this study introduces a smart hybrid glass platform as a new photo-responsive switchable system, offering versatility for a wide array of photonic applications.

Full-color, time-valve controllable and Janus-type long-persistent luminescence from all-inorganic halide perovskites.

Long persistent luminescence (LPL) has gained considerable attention for the applications in decoration, emergency signage, information encryption and biomedicine. However, recently developed LPL materials - encompassing inorganics, organics and inorganic-organic hybrids - often display monochromatic afterglow with limited functionality. Furthermore, triplet exciton-based phosphors are prone to thermal quenching, significantly restricting their high emission efficiency. Here, we show a straightforward wet-chemistry approach for fabricating multimode LPL materials by introducing both anion (Br-) and cation (Sn2+) doping into hexagonal CsCdCl3 all-inorganic perovskites. This process involves establishing new trapping centers from [CdCl6-nBrn]4- and/or [Sn2-nCdnCl9]5- linker units, disrupting the local symmetry in the host framework. These halide perovskites demonstrate afterglow duration time ( > 2,000 s), nearly full-color coverage, high photoluminescence quantum yield ( ~ 84.47%), and the anti-thermal quenching temperature up to 377 K. Particularly, CsCdCl3:x%Br display temperature-dependent LPL and time-valve controllable time-dependent luminescence, while CsCdCl3:x%Sn exhibit forward and reverse excitation-dependent Janus-type luminescence. Combining both experimental and computational studies, this finding not only introduces a local-symmetry breaking strategy for simultaneously enhancing afterglow lifetime and efficiency, but also provides new insights into the multimode LPL materials with dynamic tunability for applications in luminescence, photonics, high-security anti-counterfeiting and information storage.

Multivalent Sulfur Vacancy-Rich NiCo2 S4 @MnO2 Urchin-Like Heterostructures for Ambient Electrochemical N2 Reduction to NH3.

Innovative advances in the exploitation of effective electrocatalytic materials for the reduction of nitrogen (N2 ) to ammonia (NH3 ) are highly required for the sustainable production of fertilizers and zero-carbon emission fuel. In order to achieve zero-carbon footprints and renewable NH3 production, electrochemical N2 reduction reaction (NRR) provides a favorable energy-saving alternative but it requires more active, efficient, and selective catalysts. In current work, sulfur vacancy (Sv)-rich NiCo2 S4 @MnO2 heterostructures are efficaciously fabricated via a facile hydrothermal approach followed by heat treatment. The urchin-like Sv-NiCo2 S4 @MnO2 heterostructures serve as cathodes, which demonstrate an optimal NH3 yield of 57.31 µg h-1  mgcat -1 and Faradaic efficiency of 20.55% at -0.2 V versus reversible hydrogen electrode (RHE) in basic electrolyte owing to the synergistic interactions between Sv-NiCo2 S4 and MnO2 . Density functional theory (DFT) simulation further verifies that Co-sites of urchin-like Sv-NiCo2 S4 @MnO2 heterostructures are beneficial to lowering the energy threshold for N2 adsorption and successive protonation. Distinctive micro/nano-architectures exhibit high NRR electrocatalytic activities that might motivate researchers to explore and concentrate on the development of heterostructures for ambient electrocatalytic NH3 generation.

A flexible ligand and halogen engineering enable one phosphor-based full-color persistent luminescence in hybrid perovskitoids.

Color-tunable room temperature phosphorescent (RTP) materials have raised wide interest due to their potential application in the fields of encryption and anti-counterfeiting. Herein, a series of CdX2-organic hybrid perovskitoids, (H-apim)CdX3 and (apim)CdX2 (denoted as CdX-apim1 and CdX-apim2, apim = 1-(3-aminopropyl)imidazole, X = Cl, Br), were synthesized using apim with both rigid and flexible groups as ligands, which exhibit naked-eye detectable RTP with different durations and colors (from cyan to red) by virtue of different halogen atoms, coordination modes and the coplanar configuration of flexible groups. Interestingly, CdCl-apim1 and CdX-apim2 both exhibit excitation wavelength-dependent RTP properties, which can be attributed to the multiple excitation of imidazole/apim, the diverse interactions with halogen atoms, and aggregated state of imidazoles. Structural analysis and theoretical calculations confirm that the aminopropyl groups in CdCl-apim1 do not participate in luminescence, while those in CdCl-apim2 are involved in luminescence including both metal/halogen to ligand charge transfer and twisted intramolecular charge transfer. Furthermore, we demonstrate that these perovskitoids can be applied in multi-step anti-counterfeiting, information encryption and smart ink fields. This work not only develops a new type of perovskitoid with full-color persistent luminescence, but also provides new insight into the effect of flexible ligands and halogen engineering on the wide-range modulation of RTP properties.

Recent progress in ion-regulated organic room-temperature phosphorescence.

Organic room-temperature phosphorescence (RTP) materials have attracted considerable attention for their extended afterglow at ambient conditions, eco-friendliness, and wide-ranging applications in bio-imaging, data storage, security inks, and emergency illumination. Significant advancements have been achieved in recent years in developing highly efficient RTP materials by manipulating the intermolecular interactions. In this perspective, we have summarized recent advances in ion-regulated organic RTP materials based on the roles and interactions of ions, including the ion-π interactions, electrostatic interactions, and coordinate interactions. Subsequently, the current challenges and prospects of utilizing ionic interactions for inducing and modulating the phosphorescent properties are presented. It is anticipated that this perspective will provide basic guidelines for fabricating novel ionic RTP materials and further extend their application potential.

Integrating Full-Color 2D Optical Waveguide and Heterojunction Engineering in Halide Microsheets for Multichannel Photonic Logical Gates.

Ensuring information security has emerged as a paramount concern in contemporary human society. Substantial advancements in this regard can be achieved by leveraging photonic signals as the primary information carriers, utilizing photonic logical gates capable of wavelength tunability across various time and spatial domains. However, the challenge remains in the rational design of materials possessing space-time-color multiple-resolution capabilities. In this work, a facile approach is proposed for crafting metal-organic halides (MOHs) that offer space-time-color resolution. These MOHs integrate time-resolved room temperature phosphorescence and color-resolved excitation wavelength dependencies with both space-resolved ex situ optical waveguides and in situ heterojunctions. Capitalizing on these multifaceted properties, MOHs-based two-dimensional (2D) optical waveguides and heterojunctions exhibit the ability to tune full-color emissions across the spectra from blue to red, operating within different spatial and temporal scales. Therefore, this work introduces an effective methodology for engineering space-time-color resolved MOH microstructures, holding significant promise for the development of high-density photonic logical devices.

Solid-State Photochemical Cascade Process Boosting Smart Ultralong Room-Temperature Phosphorescence in Bismuth Halides.

Molecular ultralong room-temperature phosphorescence (RTP), exhibiting multiple stimuli-responsive characteristics, has garnered considerable attention due to its potential applications in light-emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo-burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)-based metal-organic halide (MOH), a continuous and photo-responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi-based MOH, diverse application demonstrations, such as multi-mode anti-counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof-of-concept for the development of solid-state PCCPs that integrate photosalient effect and photochromism with light-chemical-mechanical energy conversion, but also lays the groundwork for designing new Bi-based MOHs with dynamically responsive ultralong RTP.

A 0D hybrid lead-free halide with near-unity photoluminescence quantum yield toward multifunctional optoelectronic applications.

Zero-dimensional (0D) hybrid metal halides have emerged as highly efficient luminescent materials, but integrated multifunction in a structural platform remains a significant challenge. Herein, a new hybrid 0D indium halide of (Im-BDMPA)InCl6·H2O was designed as a highly efficient luminescent emitter and X-ray scintillator toward multiple optoelectronic applications. Specifically, it displays strong broadband yellow light emission with near-unity photoluminescence quantum yield (PLQY) through Sb3+ doping, acting as a down-conversion phosphor to fabricate high-performance white light emitting diodes (WLEDs). Benefiting from the high PLQY and negligible self-absorption characteristics, this halide exhibits extraordinary X-ray scintillation performance with a high light yield of 55 320 photons per MeV, which represents a new scintillator in 0D hybrid indium halides. Further combined merits of a low detection limit (0.0853 µGyair s-1), ultra-high spatial resolution of 17.25 lp per mm and negligible afterglow time (0.48 ms) demonstrate its excellent application prospects in X-ray imaging. In addition, this 0D halide also exhibits reversible luminescence off-on switching toward tribromomethane (TBM) but fails in any other organic solvents with an ultra-low detection limit of 0.1 ppm, acting as a perfect real-time fluorescent probe to detect TBM with ultrahigh sensitivity, selectivity and repeatability. Therefore, this work highlights the multiple optoelectronic applications of 0D hybrid lead-free halides in white LEDs, X-ray scintillation, fluorescence sensors, etc.

Photo-Controllable Ultralong Room-Temperature Phosphorescence: State of the Art.

In this concept, we showcase the upsurge in the studies of dynamic ultralong room-temperature phosphorescence (RTP) materials containing inorganic and/or organic components as versatile photo-responsive platforms. The goal is to provide a comprehensive analysis of photo-controllable RTP, and meanwhile delve into the underlying RTP properties of various classes of photochromic materials including metal-organic complexes, organic-inorganic co-crystals, purely organic small molecules and organic polymers. In particular, the design principles governing the integration of the photochromic and RTP moieties within a single material system, and the tuning of dynamic RTP in response to light are emphasized. As such, this concept sheds light on the challenges and opportunities of using these tunable RTP materials for potential applications in optoelectronics, particularly highlighting their use of reversible information encryption, erasable light printing and rewritable smart paper.

Flexible Crystal Heterojunctions of Low-Dimensional Organic Metal Halides Enabling Color-Tunable Space-Resolved Optical Waveguides.

Molecular luminescent materials with optical waveguide have wide application prospects in light-emitting diodes, sensors, and logic gates. However, the majority of traditional optical waveguide systems are based on brittle molecular crystals, which limited the fabrication, transportation, storage, and adaptation of flexible devices under diverse application situations. To date, the design and synthesis of photofunctional materials with high flexibility, novel optical waveguide, and multi-port color-tunable emission in the same solid-state system remain an open challenge. Here, we have constructed new types of zero-dimensional organic metal halides (Au-4-dimethylaminopyridine [DMAP] and In-DMAP) with a rarely high elasticity and rather low loss coefficients for optical waveguide. Theoretical calculations on the intermolecular interactions showed that the high elasticity of 2 molecular crystalline materials was original from their herringbone structure and slip plane. Based on one-dimensional flexible microrods of 2 crystals and the 2-dimensional microplate of the Mn-DMAP, heterojunctions with multi-color and space-resolved optical waveguides have been fabricated. The formation mechanism of heterojunctions is based on the surface selective growth on account of the low lattice mismatch ratio between contacting crystal planes. Therefore, this work describes the first attempt to the design of metal-halide-based crystal heterojunctions with high flexibility and optical waveguide, expanding the prospects of traditional luminescent materials for smart optical devices, such as logic gates and multiplexers.

CO2-responsive tunable persistent luminescence in a hydrogen-bond organized two-component ionic crystal.

A reversible CO2-responsive luminescent material was constructed by a facile hydrogen-bond self-assembly of a two-component ionic crystal. The modification of CO2 on the ionic crystal not only alternates the green afterglow, but also endows the material with inverse excitation wavelength dependence for multicolor emission.

Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures.

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.

Layered Double Hydroxide Nanosheets Boosting Red Long Afterglow via Highly Efficient Energy Transfer.

Room-temperature phosphorescent (RTP) based long-afterglow materials have shown broad application prospects in smart sensors, biological imaging, photodynamic therapy, and many others. However, the fabrication of red long-afterglow materials still faces a great challenge due to the competitive relationship between RTP efficiency and lifetime. In this work, we reported a series of layered double hydroxide (LDHs) nanosheets with red long-afterglow (quantum yield up to 42.35% and lifetime up to 256.77 ms) by taking advantage of the highly efficient triplet-triplet energy transfer from green phosphorescent LDHs to the red fluorescent dye rhodamine B (RhB, as a guest molecule). Specifically, the Zn-based LDHs@RhB composite (Zn-Al-LDH-4-CBBA@RhB) presents energy transfer efficiency as high as 95.18%, and the red long-afterglow could even be excited upon white-light irradiation. Benefiting from the time-resolved afterglow, the LDHs@RhB composites exhibit great potential in the fields of anticounterfeiting and information encryption.

Macroscopic Assembly of Chiral Hydrogen-bonded Metal-free Supramolecular Glasses for Enhanced Color-tunable Ultralong Room Temperature Phosphorescence.

Glassy materials, with desirable mechanical rigidity, shaping ability, high transparency, are attracting great interest in diverse fields. However, optically bulk molecule-based glasses are still rare, mainly due to limited monomeric species and harsh preparation conditions. Herein, we report a facile bottom-up solution fabrication process to obtain metal-free supramolecular glasses (SMGs) at the macroscopic scale using L-Histidine and hexamethylenetetramine as building blocks. The chiral SMGs possess color-tunable ultralong room temperature phosphorescence (decay lifetime up to 141.2 ms) and circular polarized luminescence (g factor up to 8.7×10-3 ). The strong hydrogen bonds effectively drive the formation of SMGs, and provide a rigid microenvironment to boost triplet exciton generation. By virtue of excitation- and temperature-dependent ultralong phosphorescence of the SMGs, applications including multicolored displays, visual UV detection, and persistently luminescent thermometer are demonstrated.

Supramolecular glasses with color-tunable circularly polarized afterglow through evaporation-induced self-assembly of chiral metal-organic complexes.

The fabrication of chiral molecules into macroscopic systems has many valuable applications, especially in the fields of optical displays, data encryption, information storage, and so on. Here, we design and prepare a serious of supramolecular glasses (SGs) based on Zn-L-Histidine complexes, via an evaporation-induced self-assembly (EISA) strategy. Metal-ligand interactions between the zinc(II) ion and chiral L-Histidine endow the SGs with interesting circularly polarized afterglow (CPA). Multicolored CPA emissions from blue to red with dissymmetry factor as high as 9.5 × 10-3 and excited-state lifetime up to 356.7 ms are achieved under ambient conditions. Therefore, this work not only communicates the bulk SGs with wide-tunable afterglow and large circular polarization, but also provides an EISA method for the macroscopic self-assembly of chiral metal-organic hybrids toward photonic applications.

Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism.

Uncovering differences between crystalline and amorphous states in molecular solids would both promote the understanding of their structure-property relationships, as well as inform development of multi-functional materials based on the same compound. Herein, for the first time, we report an approach to leverage crystalline and amorphous states of a zero-dimensional metal-organic complex, which exhibited negative and positive photochromism, due to the competitive chemical routes between photocycloaddition and photogenerated radicals. Furthermore, different polymorphs lead to the on/off toggling of photo-burst movement (photosalient effect), indicating the controllable light-mechanical conversion. Three demos were further constructed to support their application in information encryption and anti-counterfeiting. This work provides the proof-of-concept of a state- and polymorph-dependent photochemical route, paving an effective way for the design of new dynamically responsive systems.

Hydrogen-bond organized 2D metal-organic microsheets: direct ultralong phosphorescence and color-tunable optical waveguides.

Ultralong phosphorescent materials have numerous applications across biological imaging, light-emitting devices, X-ray detection and anti-counterfeiting. Triplet-state molecular phosphorescence typically accompanies the singlet-state fluorescence during photoluminescence, and it is still difficult to achieve direct triplet photoemission as ultralong room temperature phosphorescence (RTP). Here, we have designed Zn-IMDC (IMDC, 4,5-imidazoledicarboxylic acid) and Cd-IMDC, two-dimensional (2D) hydrogen-bond organized metal-organic crystalline microsheets that exhibit rarely direct ultralong RTP upon UV excitation, benefiting from the appropriate heavy-atom effect and multiple triplet energy levels. The excitation-dependent and thermally stimulated ultralong phosphorescence endow the metal-organic systems great opportunities for information safety application and temperature-gated afterglow emission. The well-defined 2D microsheets present color-tunable and anisotropic optical waveguides under different excitation and temperature conditions, providing an effective way to obtain intelligent RTP-based photonic systems at the micro- and nano-scales.