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By using transitional metal (TM)complex cations as structure-directingagents, a series of new hybrid cuprous halides with abundant architecturesranging from one-dimensional (1D) ribbons to two-dimensional (2D)layers have been solvothermally prepared and structurally characterized.Compounds [TM(2,2-bipy)3]Cu5I7(TM= Fe (1), Co (2), and Ni (3)) feature 1D [Cu5I7]2–chainsformed by the interconnection of [Cu5I10] unitsvia edge-sharing. In compounds [TM(2,2-bipy)2I]2Cu7I9(TM = Mn (4), Cu (5), and Ru (6)), the [Cu5I9] units and [Cu2I6] dimers are alternatelyinterlinked via edge-sharing to form the 1D [Cu7I9]2–chains. Compound [Cu(2,2-bipy)2I][(Me)2-2,2-bipy]Cu8I11(7) containsa new 1D [Cu8I11]3–chaincomposed of complex [Cu8I13] units based onCuI4tetrahedra and CuI3triangles. Compound[Co(2,2-bipy)3]Cu5Br8(8) features 1D [Cu5Br8]3–anionicchain built from the interconnection of [Cu6Br10] units and linear [Cu4Br8] tetramers. In compoundK[Mn(2,2-bipy)3]2Cu6I11(9), the [Cu3I7] secondary buildingunits are directly interconnected to form 2D [Cu6I11]5–layers, which are further interconnectedby K+ions via weak K–I bonds to generate a 3D [K@Cu6I11]4–framework with 1D largechannels occupied by [Mn(2,2-bipy)3]2+complexes.The UV–vis diffuse reflectance measurements reveal that thetitle compounds possess semiconductor behaviors with smaller bandgaps of 1.44–1.95 eV, and samples 4, 5, and 9show highly efficient photocatalytic degradationactivities over organic pollutant than N-doped P25 under visible-lightirradiation. [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]

Although the luminescent performance of organic–inorganic metal halides (OIMHs) have obtained significant advances, achieving intrinsic water‐stable OIMHs remain a substantial challenge due to the fragile ionic nature of hybrid the halide structure. To overcome these challenges, a structural design strategy is proposed that involves the use of highly hydrophobic cations as a protective layer to improve the water stability of OIMH. Herein, an aprotic trimethylsulfoxonium [TMSO]+ is selected as a hydrophobic cation and successfully assemble two new manganese based OIMHs of (TMSO)MnCl3 and (TMSO)MnBr3 through facile solid and liquid phase reaction methods. Remarkably, these halides exhibit strong red light emissions with high quantum yields recorded at 86.1% and 53.4%, respectively, originating from the octahedral [MnX6]4− based one‐dimensional (1D) [MnX3]− chain. Most significantly, these halides present extraordinary structural and luminescent stabilities toward continuous corrosion by humid air, water, and acid‐aqueous solution for more than one month, suggesting promising application prospects in extreme chemical environments. In‐depth Hirshfeld surface calculations demonstrate that the ultrahigh water‐stability benefits from the abundant hydrogen bonds and strong electrostatic interactions between [TMSO]+ and [MnX3]− ions, which provides an underlying insight into the stability mechanism. This water‐stability enhancement strategy represents a breakthrough structural engineering to rationally design more water‐stable OIMH. [ABSTRACT FROM AUTHOR]

Considering the instability and toxicity of 3D Pb-based perovskite nanocrystals, lead-free low-dimensional organic–inorganic hybrid metal halides have attracted widespread attention as potential substitutes. Herein, two new tin-based 0D halides [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O (BAPP = 1,4-bis(3-aminopropyl)piperazine) were synthesized successfully based on [SnX5]3− as an emission center. Typically, [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O display broadband yellow and yellow-green light emissions originating from the radiative recombination of self-trapped excitons (STEs). The photoluminescence quantum yields (PLQYs) of the two compounds were calculated to be 19.27% and 2.36%, respectively. Furthermore, the excellent chemical and thermal stability and broadband light emissions reveal their potential application in solid-state white lighting diodes. [ABSTRACT FROM AUTHOR]

Environmentally friendly and highly efficient blue luminescent materials are an unremitting pursuit in the optoelectronic field. Herein, we assembled a new 0D lead-free metal halide of (F-PPA)ZnBr4, which exhibits narrow blue light emission with a remarkable PLQY of 50.15%, high stability and high detection sensitivity toward UV light. These results indicate the potential for the application of low-dimensional zinc-based halides in multiple optoelectronic devices. [ABSTRACT FROM AUTHOR]

Despite the ultra‐high photoluminescence quantum yield (PLQY) of 0D hybrid manganese halides as state‐of‐the‐art luminescent materials, intrinsic water stability remains an unsurpassable barrier due to the serious hygroscopicity of the hydrogen‐bonding structure. Herein, a synthetic strategy that realizes adjustable emission color and high water resistance in a 0D hybrid manganese chloride family based on the same cation of [H2TMDAP]2+ (TMDAP = N,N,N′,N′‐tetramethyl‐1,3‐diaminopropane) is reported. Specifically, direct solution or solid‐state reaction of precursor materials generates [H2TMDAP]3[MnCl4]2[Mn2Cl6], while additional Zn2+‐doping as a structural directing agent results in [H2TMDAP]Mn0.63Zn0.37Cl4. Functionally, the [Mn/ZnCl4]2− tetrahedron based [H2TMDAP]Mn0.63Zn0.37Cl4 displays green light emission at 521 nm with a PLQY of 63.9%. [H2TMDAP]3[MnCl4]2[Mn2Cl6] is composed of a [MnCl6]4− octahedron based [Mn2Cl6]2− chain and a discrete [MnCl4]2− tetrahedron, but it only exhibits single red emission at 628 nm with a PLQY of 48.1%. Compared with water‐instable [H2TMDAP]Mn0.63Zn0.37Cl4, [H2TMDAP]3[MnCl4]2[Mn2Cl6] represents extraordinary chemical stability in humid air and water over 1 month, manifested by an unchanged structural lattice and sufficient emission intensity. Significantly, the ultra‐high water proof performance of [H2TMDAP]3[MnCl4]2[Mn2Cl6] is nearly unmatchable among all previously reported manganese halides as far as is known. The combined merits of tunable emission wavelength, high PLQY, and stability highlight the potential applications of title materials in solid‐state lighting and display diodes. [ABSTRACT FROM AUTHOR]

In the relentless pursuit of developing high-performance, stable and environmentally friendly materials for X-ray detection, we present a new class of Bi-based hybrid organic–inorganic perovskites. An X-ray detector based on a new zero-dimensional (0D) triiodide-induced lead-free hybrid perovskite, (DPA)2BiI9 (DPA = C5H16N22+), has been developed demonstrating outstanding detection performance, including high X-ray sensitivity (20 570 μC Gyair−1 cm−2), low detectable dose rate (0.98 nGyair s−1), fast response time (154/162 ns) and excellent long-term stability. [ABSTRACT FROM AUTHOR]

Recently, zero‐dimensional (0D) hybrid metal halides have attracted intensive attention with wide applications in solid‐state lighting and display diodes. Herein, by using a facile wet‐chemistry method, we prepared one new 0D hybrid antimony halide of [HMHQ]2SbCl5 ⋅ 2H2O (MHQ=2‐methyl‐8‐hydroxyquinoline) based on the discrete [SbCl5]2− unit. Remarkably, the bulk crystals of [HMHQ]2SbCl5 ⋅ 2H2O exhibit strong cyan light emission with a promising photoluminescence quantum yield (PLQY) of 18.92%. Systematical studies disclose that the cyan emission is mainly derived from the radiative recombination within conjugated organic cation. Benefiting from the promising luminescent performance, this 0D antimony halide can be utilized as an excellent down‐conversion light emitting luminescent material to assemble white light‐emitting diodes with high color rendering index (CRI) of 90.2. [ABSTRACT FROM AUTHOR]

Despite remarkable luminescent performance of 0D lead halide perovskites, achieving highly efficient blue light emission is extremely challenging and crucial for this domain. Considering the high toxicity of Pb2+ ion, it is significant to explore water‐stable lead‐free 0D halides as highly efficient and stable blue emitting materials. To address these issues, a family of 0D hybrid zinc halides of AZnBr4 (A = EP, BP, and TMPDA) based on discrete [ZnBr4]2− tetrahedrons is herein reported as desirable blue light emitters. The wide band gaps enable these 0D halides to display highly efficient blue light emissions (452–485 nm) with highest photoluminescence quantum yield (PLQY) of 35.47%. More importantly, all these 0D halides present extraordinary chemical stabilities in humid air and water for one month, and are also capable of withstanding extreme pH conditions in the range of 0–14, likely the widest observed pH range for perovskites. Notably, the ultrahigh chemical stabilities of 0D zinc halides are nearly unmatchable among all known literature perovskite materials to the best of the authors' knowledge. Combined superiorities of unusual blue light emission, promising PLQY, ultrahigh stability, and non‐toxicity highlight the potential optoelectronic applications in wide chemical environments for these 0D zinc halides. [ABSTRACT FROM AUTHOR]

Two new zero-dimensional (0D) hybrid indium halides of [H2DMP]2InX7·2H2O (X = Cl, Br) were designed based on [InX6]3− octahedra as optically active centers. Remarkably, these 0D halides display intrinsic broadband yellow-orange light emissions with highest quantum yield of 58.53% exceeding all previously reported 0D indium halides. [ABSTRACT FROM AUTHOR]

X-ray detection plays an extremely significant function in medical diagnosis, nondestructive testing, safety testing, scientific research, environmental monitoring and other practical applications. However, conventional inorganic semiconductors, such as amorphous selenium, crystalline Si and pure Ge present almost uncontrollable bandgaps and require quite sophisticated fabrication techniques despite their outstanding performance. As developing materials for direct conversion X-ray detection, halide perovskite semiconductors exhibit remarkable properties with high sensitivity. In this review, we summarize the optoelectronic performance of different dimensional perovskites in X-ray detection and their application in X-ray imaging for perovskite-based X-ray detectors including single crystals, films and wafers. This review aims to preliminarily highlight the relationship between structural dimensionality and X-ray detection properties, which should provide valuable suggestions for researchers to rationally design high-performance halide perovskite X-ray photodetectors through crystal engineering at the molecular level in the future. [ABSTRACT FROM AUTHOR]

Rationally optimizing the photoluminescence performance via accurate structural modulation is one of most important and challenging issues for hybrid halides. Herein, a viable crystal dimensional reduction strategy is proposed to reasonably enhance the photoluminescence quantum yield (PLQY) of hybrid antimony halide. Specifically, a synthetic technique is developed and new 1D [DMPZ]SbCl5 ∙ H2O (DP‐SbCl5) is sliced to 0D [DMPZ]2SbCl6 ∙ Cl ∙ (H2O)2 (DP‐SbCl6) with crystal dimensional reduction from infinite [SbCl5]2− chain to discrete [SbCl6]3− octahedron. Comparing with nonluminescent 1D DP‐SbCl5, 0D DP‐SbCl6 displays highly efficient broadband yellow light emission with enhanced PLQY up to 75.94%. First‐principles calculation demonstrates that 0D DP‐SbCl6 features more flat and narrow band structure, which promotes the photoelectron localization and increases the quantum confinement, and finally boosts the luminescence efficiency. Together highly efficient and ultra‐stable luminescence performance enable DP‐SbCl6 as excellent down‐conversion broadband yellow phosphor to successfully fabricate white light emitting diodes with a high color rendering index of 92. This work provides a novel structural modulation strategy of crystal dimensional reduction to rationally optimize the PL performance of hybrid metal halides. [ABSTRACT FROM AUTHOR]

Five new zero-dimensional hybrid manganese halides based on discrete [MnCl4]2− tetrahedrons were prepared and used as highly efficient green-light emitters. Through rational management of organic cations to tailor the Mn⋯Mn separation distances between neighboring [MnCl4]2− tetrahedrons, the photoluminescence quantum yield increased significantly from 7.98% to 81.11%. [ABSTRACT FROM AUTHOR]

One new type of hybrid lead halide of [DTHPE]2Pb3Cl10 has been synthesized and characterized containing a one-dimensional (1D) wavelike [Pb3Cl10]4− chain based on a corner-shared [Pb3Cl11] cluster. Remarkably, this cluster-based 1D chain displays intrinsic broadband white light emission with a high quantum efficiency of 19.45% exceeding those of previously reported typical two-dimensional perovskites. [ABSTRACT FROM AUTHOR]

Herein, by using a structural design strategy of incorporating hetrometallic halide blocks, we prepared the first 3D bimetallic halide of [H2DABCO]2Cu6PbBr12 with new topological network based on two types of 6-connected nodes. Remarkably, this 3D framework displays highly efficient thermochromic luminescence from broadband yellow to green light emissions with remarkable stability. [ABSTRACT FROM AUTHOR]

Low-dimensional hybrid antimony halide perovskites have fascinated the extensive research for their excellent photoluminescence behaviors. However, reasonable optimization of luminescence performance through molecule-level structural regulation remains a formidable challenge. The solution evaporation method with the reaction of organic amines and acid solutions of metal salts is a well-established method for the synthetic of low-dimensional hybrid antimony halide. In this work, by selecting organic cations with different sizes as template molecules, we have successfully synthesized three hybrid antimony halides of 0D [HDBA] 2 SbCl 5 (1), 0D [H 2 ATMP] 2 SbCl 7 (2) and 1D [H 3 PMDETA]Sb 2 Cl 9 (3) (DBA ​= ​dibutylamine, ATMP ​= ​4-amino-2,2,6,6-tetramethylpiperidine, PMDETA = N,N,N′,N″,N″-pentamethyldiethylenetriamine). by the solution evaporation method at room temperature for 2–5 days. These hybrid antimony halides exhibit broadband yellow-light with the highest photoluminescence quantum yield (PLQY) of 8.38%. According to detailed spectroscopy characterizations and theoretical calculations, the broadband light emissions should originate from self-trapped excitons (STEs). These antimony halides could be fabricated as white LEDs with highest color rendering index (>90%). The intrinsic broad-band light emissions and facile assembly process enable these hybrid antimony halides as promising candidates for yellow-light emitting materials. Structural design of hybrid antimony halide : Three antimony chlorides with different structures were prepared by facile solution method. These antimony chlorides have 0D pyramidal [SbCl 5 ]2- and 1D [Sb 2 Cl 9 ]3- chains, and display the broadband yellow-light emissions. [Display omitted] • Lead-free hybrid antimony halides with 0D pyramidal [SbCl 5 ]2- and 1D [Sb 2 Cl 9 ]3- chains. • Broadband yellow-light emissions originate from self-trapped excitons. • These hybrid antimony halides can be fabricated as white LEDs with high CRI. [ABSTRACT FROM AUTHOR]

New 2D perovskites contain special 2D layers formed by the mix of corner- and edge- shared with [PbX 6 ] octahedrons, and display the broadband yellow-light emissions covering the whole visible region. [Display omitted] • New 2D perovskites composed of mixed corner- and edge-shared octahedron. • Broadband emission covering the whole entire visible light. • These 2D perovskites can be fabricated as white LEDs with high CRI. Herein, we reported two new 2D perovskites of [DAPMA] 2 Pb 3 X 12 ·2H 2 O (X = Cl (1), Br (2), DAPMA = N,N-Bis(3-aminopropyl)methylamine) containing special 2D [Pb 3 X 12 ]6− layers formed by mixed corner- and edge-shared [PbX 6 ] octahedrons. Both compounds 1 and 2 exhibit broadband yellow light emissions with promising photoluminescence quantum yields of 4.84% and 3.02%, respectively. According to detailed spectroscopy characterizations, the broadband light emissions should originate from self-trapped excitons (STEs). In addition, these 2D perovskites can be fabricated as white LEDs with highest color rendering index of 96.3%. This work provides a new type of structural model to probe into the relationship between luminescence behavior and structure. [ABSTRACT FROM AUTHOR]

One new bulk lead-free 0D antimony halide of [DPA] 3 SbCl 6 was designed as greenish-yellow light emitter with near-unity PLQY. Thorugh elaborate fabrication toward [DPA] 3 SbCl 6 , multiple reversible photoluminescence on/off switch was achieved with important potential in anti-counterfeiting and confidential information encryption-decryption technologies, which opens a new way to design perovskite materials for new optoelectronic applications. [Display omitted] • New 0D antimony halide as efficient green emitter with remarkable near-unity PLQY. • Applied as luminescent ink against high-resolution anti-counterfeiting application. • Fast information encryption decryption achieved through solid/liquid dual mode. • Multiple reversible PL on/off switches enhancement information encryption decryption. Storage and protection of confidential information is an increasing challenge for global digital economy, which stimulates the never-ending pursuit of high-security technology to prevent information forgery and leakage. Herein, we develop a novel approach to realize controllable information encryption-decryption based on reversible photoluminescence (PL) on/off switch in 0D hybrid antimony halide. A new 0D [DPA] 3 SbCl 6 (DPA = dipropylamine) was designed as broadband green light emitter with near-unity photoluminescence quantum yield. Benefiting from invisible and non-luminescent superiorities of SbCl 3 , information encrypted by SbCl 3 pattern can′t be directly decoded upon common light excitations. Under the trigger of [DPA]Cl salt, superfast transition from SbCl 3 to [DPA] 3 SbCl 6 gives rise to highly efficient emission and thus effective information decoding. Subsequently, through methanol impregnation and desolvation strategy, luminescence of [DPA] 3 SbCl 6 can be easily quenched and recovered resulting in reversible PL on/off switching. The multiple and controllable PL emission conversion provides a dual-mode confidential information encryption-decryption technology. [ABSTRACT FROM AUTHOR]