Search

A new one-dimensional hybrid [APCHA]Cu2I4 was designed and applied as an X-ray scintillator. It exhibits broad-band green emission with a high PLQY of 74.80% and excellent stability. It demonstrates radioluminescence property with a light yield of 28 336 photons MeV−1, detection limit of 41 nGyair s−1, and high spatial limit of 13.95 lp mm−1 in X-ray imaging. [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]

Herein, we for the first time report a reversible conversion between green-emissive [DMPZ]MnCl4 and red-emissive [DMPZ]4(MnCl6)(MnCl4)2·(H2O)2 (DMPZ = 1,4-dimethylpiperazine) using kinetic and thermodynamic controlling strategies. Significantly, the synchronous structural and emission transformations in single-component organic manganese halides with adjustable emission colors are highlighted. [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]

Immunogenic cell death (ICD) induced by reactive oxygen species (ROS) represents a particular form of tumor cell death for approaching the problem of low immunogenicity of tumors in immunotherapy, while the oxidative damage to normal cells of current ICD inducers hinders their clinical application. Herein, a new ICD inducer VC@cLAV constructed solely by dietary antioxidants, lipoic acid (LA) and vitamin C (VC), is developed, which could promote heavy intracellular ROS production in cancer cells for ICD induction while acting as an anti-oxidant in non-cancer cells for cytoprotection, and thus hold high biosafety. In vitro studies show that VC@cLAV induced a release of antigens and a maturation rate of DCs up to 56.5%, approaching the positive control (58.4%). In vivo combined with aPD-1, VC@cLAV showed excellent antitumor activity against both primary and distant metastatic tumors with an inhibition rate of 84.8% and 79.0% compared to 14.2% and 10.0% in the aPD-1 alone group. Notably, VC@cLAV established a long-term antitumor immune memory effect against tumor rechallenging. This study not only presents a new kind of ICD inducer but also provides an impetus for the development of dietary antioxidant-based cancer drugs. [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]

Hybrid organic–inorganic lead halide perovskites (HOIPs) possess significant photoelectric characteristics for solar energy conversion, but the presence of lead causes issues for eco-friendly applications. Halide double perovskites represent a green option for application in the optoelectronic field, especially X-ray detection systems. Despite the great efforts, the exploration of large-size lead-free iodide-based hybrid double perovskite single crystals for X-ray detection has been unsuccessful. Herein, we demonstrate that a large single crystal of the 2D (two-dimensional) semiconducting perovskite (C6H16N2)2CuBiI8·0.5H2O can serve as an X-ray detection candidate. A perovskite crystal, as large as 35 × 31 × 3 mm3, was grown using a low-cost, simple cooling solution approach. To the best of our knowledge, this is the first time a centimeter-sized 2D BiCu iodide double perovskite single crystal has been used for X-ray detection. The perovskite crystal exhibited unique properties for X-ray detection, such as a significant X-ray absorption coefficient, considerable μτ product, and low trap density. Moreover, X-ray detection with a sensitivity of 5.51 μC Gyair−1 cm−2 was achieved based on a single crystal. This work opens new ways to explore specially designed organic cations for stabilizing 2D HOIPs that show great potential in optoelectronics. [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]

The concentration-caused quenching (CCQ) effect seriously deteriorates the photoluminescence (PL) efficiency of 0D organic–inorganic hybrid halide perovskites but reasonable management of CCQ via accurate structural design strategies remains a formidable challenge for PL property optimization. Herein, by fine-tuning the geometric configurations of organic cations, a controllable PL quenching-activation switch is realized by accurately modulating the CCQ effect. Specifically, we rationally designed a couple of 0D antimony halides, namely [BPP]SbCl5 (BPP = 1,3-bis(4-pyridyl)-propane) and [BPPP]SbCl5 (BPPP = 1,3-bis(4-piperidyl)-propane), based on the same [SbCl5]2− units. Through purposive structural regulation from the closely confined [BPP]2+ to the incompact [BPPP]2+ matrix, the concentration of the fluorescent [SbCl5]2− species and the CCQ effect were notably diminished, which significantly promoted the localization degree of the photoelectrons. Hence, [BPPP]SbCl5 displays enhanced broadband yellow light emission with a high photoluminescence quantum yield of 79.57%, while [BPP]SbCl5 is completely non-luminescent. In addition, by virtue of the PL inactivation–activation conversion in the superfast assembly process from SbCl3 to [BPPP]SbCl5, secret information encrypted by an invisible printed SbCl3 pattern can be rapidly decrypted by the light-emissive [BPPP]SbCl5 under the trigger of an organic precursor, which showcases the potential in confidential information encryption–decryption technology. [ABSTRACT FROM AUTHOR]

An ultrapure green phosphor with narrow emission range (525–535 nm) and full width at half maximum (FWHM < 25 nm) is critical for a backlit light-emitting diode to realize an ultrawide color gamut in liquid-crystal display (LCD), according to the Rec. 2020 standard. However, it is extremely formidable to achieve this goal for low-dimensional halide perovskites (LDHPs), which readily display broadband emissions arising from self-trapped excitons due to strong electron–phonon coupling. Herein, we report a new one-dimensional (1D) hybrid lead halide of [TMPDA]2Pb3Br10 (TMPDA = tetramethyl-1,3-diaminopropane) displaying unusual ultrapure green light emission. Benefiting from the synergistic work of weak electron–phonon interaction and strong quantum confinement, this 1D halide displays sharp green emission at 526 nm with narrow FWHM (25 nm), high photoluminescence quantum yield (71.95%) and color purity (91.1%), which achieves the Rec. 2020 standard and represents the purest green emitting LDHP to date. Remarkably, as a down-conversion green phosphor, [TMPDA]2Pb3Br10 provides an ultrawide color gamut covering 121.5% of NTSC and 90.7% of Rec. 2020 standards, showcasing the application in high-resolved LCD. The establishment of a fundamental structure–property relationship also paves a new way to rationally design novel narrow-band emitting LDHPs as a supplement of colloidal 3D perovskite nanostructures. [ABSTRACT FROM AUTHOR]

A facile, green and economical preparation technique is critical for the cost-effective scale-up manufacture and optoelectronic device engineering of halide perovskites. Herein, we developed a viable solvent-free mechanochemical synthetic route to systematically prepare organic–inorganic hybrid perovskites. In this work, an enormous halide library comprising 16 zero-dimensional hybrid manganese halides with the formula of AnMnX4 (A = organic cations, X = Cl, Br, n =1, 2) was synthesized through an economically and environmentally friendly mechanical grinding solid-state reaction within a quite fast time of 40 s and 100% yield. Even without any crystallization process, these AnMnX4 display strong green light emissions with the highest photoluminescence quantum yield (PLQY) of 79.5%, which reaches up to the top rank of green-light-emitting halide perovskites. Moreover, the enormous structural library facilitates us to build up a direct correlation between intermolecular Mn⋯Mn distances and PLQY, which provides a feasibility of fine-tuning luminescence performance by reasonably managing organic species to tailor the Mn⋯Mn distance. This work not only paves a green assembly way of hybrid perovskite materials but also provides a generalized method to rationally optimize the luminescence performances of hybrid manganese halides, which is potentially extended to all emissive 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]

Recently, low-dimensional organic–inorganic hybrid metal halides have attracted considerable attention in solid-state optical application fields, especially in white-light emitting diodes (WLEDs) owing to intrinsic broadband luminescence performances. Herein, by selecting different types of organic cations as a structural decoration strategy, we designed a series of new 1D hybrid halides of A2Pb3Br10 (A = NPM, DMPDA, TMEN) based on same [Pb3Br10]4− chains composed of edge-shared [Pb3Br12]6− trimers. The low-dimensional crystal lattice results in the formation of self-trapped excitons, which leads to broadband light emissions covering the entire visible region for all A2Pb3Br10 homologues. Specifically, compound 1 exhibits yellowish-white light emission (0.34, 0.45) with a photoluminescence quantum efficiency of 2.51%. Both compounds 2 and 3 show bluish-white light emissions centered at 438 nm and 440 nm, respectively, with high color rendering index (CRI) of 96, which belongs to one of the highest values to date. The intrinsic broadband white light emissions enable them as promising candidates for single-component white-light emitting materials. [ABSTRACT FROM AUTHOR]

It remains significant to explore new types of hybrid lead halides to realize the diversifications of structural and luminescence properties due to the excellent optoelectronic performances of perovskites. Herein, by choosing various organic molecules as cationic templates, we constructed a series of new one-dimensional (1D) lead halide perovskites, namely, [DMEDA]Pb2Br6·H2O (1), [ATMPD]Pb2Br6·H2O (2) and [TMPrDA]2Pb3X10 (3: X = Br; 4: X = Cl). The crystal structures of compounds 1–4 contain 1D [Pb2Br6]2− and [Pb3X10]4− chains based on [Pb4X16] tetramer clusters as basic building units, respectively. Remarkably, compound 2 displays broadband yellow light emissions spanning the entire visible spectral range and centered at 534 nm, which can be ascribed to self-trapped excitons based on systematic characterization including time-resolved PL emission and theoretical studies. This work provides a series of new low-dimensional hybrid lead halides as prototypes to enrich the halide chemistry including crystal engineering and optoelectronic performance. [ABSTRACT FROM AUTHOR]

Pursuits of high-performance blue light-emitting perovskites have attracted intensive attention due to an insufficient photo-luminescence quantum yield (PLQY) of <5% for CsPbCl3, which far lags behind the near-unit PLQYs (>90%) in the green and red emission spectral regions of CsPbX3 (X = Br and I), respectively. Hence, it is very significant to improve the blue light emitting PLQYs to balance the development of three-primary-colour in high-definition displays. In this study, we have proposed a new structural design strategy of reducing the lattice dimension to enhance quantum confinement effect and further improve the blue-light emission efficiency. Herein, by rationally choosing a long chain-like organic cation to slice the [PbCl3]− skeleton, we have successfully constructed the first 0D perovskite of [BAPrEDA]PbCl6·(H2O)2, in which the isolated [PbCl6]4− units are confined by a closely assembled organic matrix. As expected, the bulk crystals of the 0D perovskite display broadband blue-violet light emission (392 nm) of radiative transition arising from triplet exciton states. Remarkably, the synergistic effects of enhanced quantum confinement and highly localized excitons from the 0D perovskite significantly boost the PLQY of blue light emission to 21.3%, which far exceeds than that of the typical 3D CsPbCl3. To the best of our knowledge, this study first realizes the lowest-dimensional structural transformation from 3D perovskite to 0D molecule but holding the intrinsic blue light emission, and it also represents a new record of highest-energy blue-violet light emission in single-crystalline 0D metal halides. [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]

In recent years, organic–inorganic hybrid metal halides have emerged as a highly promising class of semiconducting light emitting diodes (LEDs) due to their fascinating photoluminescence properties. Here, by specifically selecting different organic cations as templates, a series of new hybrid cuprous halides have been solvothermally prepared, namely [Me-Py]CuI2 (1), [(Me)2-DABCO]Cu2I4 (2), [Me-MePy]Cu2I3 (3), and [H2DABCO]Cu3X5 (X = I (4) and Br (5)). These hybrid cuprous halides feature one-dimensional (1D) [CuI2]−, [Cu2I3]− and [Cu3X5]2− (X = Br, I) chains surrounded and charge-balanced by organic cations. Under UV photoexcitation, these hybrid cuprous halides exhibit strong tunable photoluminescence from cyan (480 nm) to red (675 nm) emissions with large Stokes shifts (345 nm). The intrinsic nature of PL emissions is also investigated based on temperature-dependent PL emission, lifetime, photoluminescence quantum efficiencies, etc. [ABSTRACT FROM AUTHOR]

Here, we prepared the first series of 3D hybrid iodoplumbates with novel porous frameworks of [Pb8I21]5− directed by transition metal complex (TMC) cationic dyes of [TM(2.2-bipy)3]2+. The microporous materials exhibit outstanding visible light-driven photoelectric properties due to the effective photosensitization of the TMC dyes. The coexistence of stronger face- and weaker corner-shared connecting manners affords the feasibility of tailoring the 3D framework into low-dimensional skeletons, which provide a new structural prototype to modify the semiconducting properties similar to those of classic perovskites. [ABSTRACT FROM AUTHOR]

Droplet evaporative crystallization on a micro-structured platform with limited interfacial area has potential applications in crystallization theory, bioengineering, and particle drug preparation. Here, an efficient and versatile approach is discussed for multiple drop-evaporative crystallization processes on a micro-crystallization chip fabricated via three-dimensional printing. A chip with limited interfacial area could be fabricated on a highly controlled crystallizer interface. During liquid injection, various drop locations and evaporative conditions can be used, which enables flexible and distinct crystallization processes. This reveals controlling mechanisms and identifies nucleation locations and growth paths. Various classic crystallization systems were introduced to evaluate the chip performance. Controlled nucleation and growth mechanisms at stable evaporative rates were revealed. From the final crystal morphologies, particle locations, and distributions, the effects of the initial concentration and droplet contact conditions at the triple-phase interface could be investigated with high adjustability. Moreover, the results can provide insights into the ‘coffee ring’ formation during evaporative crystallization, dendritic crystal growth, and hydrate crystallization mechanisms. In the limited microstructure, the capillary flow of a liquid drop can spontaneously drive the crystal distribution and morphology. Finally, incorrect liquid drop locations that led to unpredictable crystal formation and distributions were discussed to improve repeatability and efficiency. Applications include the manufacture of particle drugs and flow chemistry. [ABSTRACT FROM AUTHOR]

Metal–organic framework (MOF)-based asymmetric heterogeneous catalysts have attracted increasing attention; however, some challenges need to be addressed, such as the rigidity of chiral auxiliary groups within MOFs and the lack of a versatile methodology for the facile construction of chiral MOFs. To address this issue, in this study, a mechanistically distinct approach was developed for heterogenizing linear chiral catalysts in the MOF cavities, rather than the synthetic modification of MOFs. This strategy involves the facile in situ polymerization of pre-impregnated chiral monomers within MOFs, affording the hybrid composites featuring a locally homogeneous and globally heterogeneous structure. The introduced chiral catalytic sites would be flexible in the pores, offering an opportunity to exploit its cooperative effect with the nearby catalytic metal nodes. The advantages of the chiral polymer/MOF composites were clarified by their excellent diastereo- and enantioselectivities and recycling capacity for catalyzing the asymmetric Aldol reaction, which were superior to those of individually heterogeneous and homogeneous catalysts. [ABSTRACT FROM AUTHOR]

By using transition-metal (TM) complex cationic dyes as structure-directing agents and photosensitizers, a series of inorganic–organic hybrid metal halides, namely, [TM(2,2′-bipy)3]AgPb2I7 [TM = Ni (1), Co (2) and Zn (3)], [Co(2,2′-bipy)3]CuPb2Br7 (4) and [TM(2,2′-bipy)3]AgPb2Br7 [TM = Ni (5) and Fe (6)], have been solvothermally prepared and structurally characterized. Compounds 1–3 feature 1D [AgPb2I7]2− chains built from the condensation of [Ag2I6] dimers and [Pb4I14] tetramers, and compounds 4, 5 and 6 contain similar 1D [CuPb2Br7]2− and [AgPb2Br7]2− chains, respectively. UV-Vis diffuse reflectance measurements reveal narrow band gaps of 1.75–2.18 eV for compounds 1–6, which lead to efficient and stable photocatalytic degradation activities over organic pollutants under visible light irradiation. Among the title compounds, sample 5 shows the highest photocatalytic degradation activity. The possible mechanism for their stable photocatalytic activities is proposed based on the experimental and theoretical studies. [ABSTRACT FROM AUTHOR]

By using 1,3-di(4-pyridyl)-propane (dpp) as templates or structure-directing agents (SDAs), a series of hybrid cuprous halogenides, namely, [H2dpp]2[Cu4I8]·H2O (1), [H2dpp][Cu2I4] (2), [H2dpp]2Cu11I15 (3) and [H2dpp]2Cu11Br15 (4), have been solvothermally prepared and structurally characterized. Despite the similar chemical compositions, compound 1 features a zero-dimensional (0D) [Cu4I8]4− unit and compound 2 contains one-dimensional (1D) [Cu2I4]2− chains, which are both separated by [H2dpp]2+ organic cations. Compounds 3–4 contain two-dimensional (2D) microporous [Cu11X15]4− (X = I, Br) layers composed of the [Cu9X17] unit interconnected by [CuX4] tetrahedra. The UV-vis diffuse-reflectance measurements reveal that the compounds 3–4 exhibit semiconducting behaviors with narrow band gaps of 1.48 and 2.21 eV, respectively, which lead to efficient photocatalytic degradation activities over an organic pollutant under visible light irradiation. The possible photocatalytic mechanism is also proposed based on experimental and theoretical studies. Furthermore, compound 1 shows interesting photochromism behavior maybe owing to the photo-induced intermolecular charge transfer. [ABSTRACT FROM AUTHOR]

With similar transition metal (TM) complex cations as structural directing agents (SDAs), six new hybrid lead bromides were synthesized and structurally characterized as [Co(2,2-bipy)3]2{[Co(2,2-bipy)]3Pb7Br24} (1), [Co(2,2-bipy)2Br]PbBr3 (2), [TM(phen)3]Pb2Br6 (TM = Co (3) and Ni (4)), [Co(2,2-bipy)3]Pb3Br9 (5) and [Co(2,2-bipy)3]Pb5Br13·CH3CN (6) with distinct structural types from zero-dimensional (0D) unit, one-dimensional (1D) chain to two-dimensional (2D) layer. Compound 1 contains the 0D {[Co(bipy)]3Pb7Br24}4− units built from the [Pb7Br24] ring attached by three unsaturated [Co(2,2-bipy)]2+ complexes via Co–Br bonds. Under the direction actions of different SDAs, compounds 2 and 3–4 contain two different types of [Pb2Br6]4− chains based on the same octahedral [PbBr6] units but with distinct connecting manners, respectively. Using the same [Co(2,2-bipy)3]3+ as SDA, compound 5 reveals a 1D [Pb3Br9]3− double chain, whereas compound 6 features a 2D complex [Pb5Br13]3− layer. The UV/vis diffuse-reflectance measurements reveal that the title compounds feature tunable band gaps of 1.70–2.29 eV. Under the visible light irradiation, sample 6 exhibits efficient and stable photocatalytic degradation activities over organic pollutants, which mainly originates from the multi-electronic effects of the TM complex cations. A possible photocatalytic mechanism is also proposed based on the radical trapping experiments and electronic band structural calculations. [ABSTRACT FROM AUTHOR]

With a [TM(phen)3]2+ (TM = transition metal, phen = 1,10-phenanthroline) complex and N-alkylated [(Me)2-2,2′-bipy]2+ (Me = methyl, 2,2′-bipy = 2,2′-bipyridine) as cations, a series of hybrid iodoargentates, namely [TM(phen)3]2Ag3I7 (TM = Mn (1), Fe (2)), [Mn(phen)3]Ag5I7 (3) and [(Me)2-2,2′-bipy]2Ag7I11 (4), have been solvothermally prepared and structurally characterized. Compounds 1 and 2 feature isolated windmill-shaped [Ag3I7]4− trimers based on [AgI3] triangles, whereas compound 3 contains two-dimensional (2D) microporous [Ag5I7]2− layers composed of [Ag3I7] and [Ag7I13] secondary building units (SBUs) based on [AgI4] tetrahedra. In compound 4, a 2D [Ag7I11]4− slab is formed by alternating interconnection of two different types of [Ag7I12] double chains via corner-sharing with one-dimensional (1D) large channels occupied by [(Me)2-2,2′-bipy]2+ cations. UV-vis diffuse-reflectance measurements reveal that the title compounds possess semiconducting behaviors with smaller band gaps of 1.85, 1.78, 1.89 and 2.03 eV, respectively. Sample 4 shows highly efficient photocatalytic degradation activity over organic pollutants than N-doped TiO2 (P25) under visible light irradiation. Moreover, a possible mechanism for the stable photocatalytic activity is proposed based on band structure calculation. Finally, the luminescence properties and thermal stabilities of the title compounds are also studied. [ABSTRACT FROM AUTHOR]

With different transition metal (TM) complexes as structure directing agents or building units, three new multinary chalcognidometalates based on T3 supertetrahedral nanocluster of [Mn2Ga4Sn4S20]8− have been solvothermally synthesized and structurally characterized. In compound Mn2Ga4Sn4S20[Mn2(en)5]2·4H2O (1, en = ethylenediamine), the neighboring [Mn2Ga4Sn4S20]8− cores were bridged by two pairs of [Mn2(en)5]4+ complex cations via Mn–S bonds to form one-dimensional (1D) neutral chains. Compound Mn2Ga4Sn4S20[Mn(dien)2]4·2H2O (2, dien = diethylenetriamine) contained discrete [Mn2Ga4Sn4S20]8− cores separated by [Mn(dien)2]2+ cations. In compound Mn2Ga4Sn4S20[Mn(teta)]4 (3, teta = triethylenetetramine), each [Mn2Ga4Sn4S20]8− core was covalently attached by four [Mn(teta)]2+ complexes via terminal Mn–S bonds to form a neutral isolated cluster. The photocatalytic experiments indicate that compound 1 was able to degrade rhodamine B (RhB) and crystal violet (CV) under visible irradiation. Furthermore, the luminescence properties and thermal stabilities of the title compounds, as well as the second-order nonlinear optical property of 3 were also studied. [ABSTRACT FROM AUTHOR]

Three new organic–inorganic hybrid manganese thiogermanates and thiostannates, namely, [Mn(en)2]MnGeS4 (1, en = ethylenediamine), [Mn(dien)2]MnSnS4 (2, dien = diethylenetriamine) and [Mn(1,2-dap)]2Sn2S6 (3, 1,2-dap = 1,2-diaminopropane), have been solvothermally synthesized and structurally characterized. Compound 1 has a three-dimensional (3D) neutral framework composed of one-dimensional (1D) [MnGeS4]2− chains and unsaturated [Mn(en)2]2+ cations interconnected via Mn–S bonds, whereas compounds 2–3 feature 1D [MnSnS4]2− anionic chains and 1D neutral [Mn(1,2-dap)]2Sn2S6 chains, respectively. Investigation into the magnetic properties of the title compounds reveals antiferromagnetic and ferromagnetic coupling interactions between the Mn(ii) ions for compounds 1 and 3, respectively. The optical and luminescence properties, as well as the thermal stabilities, were also studied. [ABSTRACT FROM AUTHOR]

The straightforward C-H functionalization of UiO-67-dcppy materials was realized by a Pd-catalysed PSM. This novel protocol provides an efficient method for the synthesis of various functionalized MOFs, which have shown promising adsorbent ability in removing phenolic contaminates from water. [ABSTRACT FROM AUTHOR]

Two low-dimensional oxime-containing Schiff base copper(I/II) complexes with iodine--copper cluster [Cu2I4]2- bridges, namely, {[CuII4I3(pop)4]2(CuI2I4)}⋅(CH3CN)2⋅H2O (2) and [CuII4I2(pop)4(CuI2I4)⋅(CH3CN)]n (3) (Hpop = 2-(hydroxyimino)-N'-[1-(2-yridyl)ethylidene]propanehydrazone), have been synthesized from the reaction of [2 x 2] grid-like compound {[CuIII(pop)]4}2⋅4H2O (1) with equivalent CuI2I2 (iodine--copper clusters) under solvothermal conditions and characterized by elemental analysis (EA), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and X-ray single-crystal/powder diffraction. The results show that 2 is a 0-D discrete structure from an assembly of one [Cu2I4]2- unit and two [2 x 2] molecular grids (1) via µ3-I atoms coordinating to CuI/CuII atoms. However, compound 3 presents a 1-D wave-like chain, which is constructed by coordination of µ2-I atoms from [CuI2I4]2- units with CuII atoms in [2 x 2] molecular grids (1). Moreover, catalytic experiments demonstrated that compounds 2 and 3 have promising visible-light-driven catalytic activity in degrading various organic dyes. [ABSTRACT FROM AUTHOR]

Two different types of microporous lanthanide metal--organic frameworks based on pyridine-3,5-dicarboxylic acid (H2pydc) and succinic acid (H2suc), namely [Ln(pydc)(suc) 0.5⋅3H2O]⋅2H2O (type I) [Ln = Pr (1), Eu (2), Tb (3), Er (4)] and [Ln(pydc)(suc) 0.5⋅2H2O]⋅2H2O (type II) [Ln = Yb (5) and Lu (6)], have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis, thermogravimetric analyses (TGA) and powder X-ray diffraction (PXRD). Complexes 1-4 (type I structure) are isomorphous, crystallize in the monoclinic P21/c space group and present three-dimensional (3D) pillar-layered frameworks constructed from two-dimensional (2D) [Ln(pydc)]- layers and suc2- pillars with 1D rhombic channels. The isomorphous compounds 5-6 (type II structure) crystallize in the triclinic P space group and feature a 2D layer made up of 1D ladder-like [Ln(pydc)]- chains and suc2- connectors with the water molecules occupying the interlayer spaces. The results show that structural variation from I to II may be attributed to the lanthanide contraction effect. Furthermore, the sorption ability of compound 2 and the luminescence properties of compounds 2-3 are also investigated. [ABSTRACT FROM AUTHOR]

Two manganese-amine complexes incorporating thioantimonates, namely (dienH3)[(dienH)MnSb8S15]⋅H2O (dien = diethylenetriamine) (1) and [Mn(teta)(H2O)2]2[Mn(tren)]2Sb3S12⋅H3O (2, teta = triethylenetetramine, tren = tris(2-aminoethyl)amine), have been solvothermally synthesized and structurally characterized. Interestingly, the organic amines show diversiform structure-directing actions in the title compounds. In compound 1, two dien molecules exhibit partial coordination to Mn2+ ions and protonated cations, and compound 2 contains mixed tetradentate tren and teta chelating amines. The optical properties, thermal stabilities and magnetic properties have also been studied. [ABSTRACT FROM AUTHOR]

The fluorescence recognition of octahedral nanocages M-QT1(M = Co, Zn) and metallotricycle Pd-QD, that are comprised of luminescence active quinoline groups and several kinds of amide groups, on ribonucleosides was investigated. The amide groups located on the opening windows or inner surface of the polyhedra and polygon, respectively, providing special environments for the size or shape-selective dynamic molecular recognition and amplified the guest-bonding events to produce a measurable output. While the participation of the active CH moiety in hydrogen bonding interactions corresponding to these amide groups caused the M-QT1polyhedra to exhibit selectivity towards cytidine over other ribonucleosides, the possible two-fold hydrogen bonding interactions between the nucleosides and the amide groups in Pd-QDmade the tricycle show a uridine-specific response. All these results demonstrated that these metal–organic architectures having amide groups and functionalized moieties are potential luminescence chemosensors for the selective sensing of special ribonucleosides, through modifying the hydrogen-bonding interactions. [ABSTRACT FROM AUTHOR]

New functionally diverse urea-derived MOF hydrogen-bond-donating heterogeneous catalysts were achieved via postsynthetic modification, which exhibit excellent catalytic activity and very broad substrate scopes for the Friedel–Crafts alkylation reactions. [ABSTRACT FROM AUTHOR]

New Ce-based Werner type tetrahedrons were achieved for sizeselectively luminescent detection of natural carbohydrates through incorporating amide groups as both the multiple hydrogen bonding triggers and binding-signalling transductor. [ABSTRACT FROM AUTHOR]

A truncated octahedral nanocage containing amide and quinoline groups has been synthesized as an artificial chemosensor for selectively fluorescent detection of uridine over other RNA-based nucleosides. [ABSTRACT FROM AUTHOR]

Low-dimensional organic-inorganic hybrid lead halide perovskites have attracted much interest in solid-state lighting and displays, but the toxicity and instability of lead halide are obstacles to their industrial applications, which must be overcome. As an alternative, Cu(I)-based hybrid metal halides have emerged as a new type of luminescent material owing to their diversified structure, adjustable luminescence, low toxicity and low cost. Herein, we report three one-dimensional (1D) hybrid Cu(I)-based halides with the general formula ACu 2 Br 4 (A = [(Me) 4 -Pipz] 2+ and [BuDA] 2+ and [TMEDA] 2+ ). These 1D hybrid Cu(I) halides display stable broadband blue emission with maximum emission peaks in the range of 445-474 nm and the highest photoluminescence quantum yield of 37.8%. Furthermore, in-depth experimental and theoretical investigations revealed that the broadband blue emissions originate from the radiative recombination of self-trapped excitons. Most importantly, there is no structural degradation and attenuation of emission intensity even after continuously soaking these halides in water for at least two months, demonstrating their ultra-high anti-water stability. Hirshfeld surface analysis shows that a large number of weak hydrogen bonds can protect the inorganic skeleton from degradation due to water. This work provides a new strategy for the design of water-stable Cu(I)-based halides with efficient blue emission and wide potential applications in humid environments.

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 [H 4 BAPP]SnBr 5 ·Br and [H 4 BAPP]SnCl 5 ·Cl·H 2 O (BAPP = 1,4-bis(3-aminopropyl)piperazine) were synthesized successfully based on [SnX 5 ] 3- as an emission center. Typically, [H 4 BAPP]SnBr 5 ·Br and [H 4 BAPP]SnCl 5 ·Cl·H 2 O 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.

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)InCl 6 ·H 2 O 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 Sb 3+ 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 μGy air 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., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)