Search

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

The modification of inorganic two‐dimensional (2D) materials with organic functional motifs is in high demand for the optimization of their properties, but it is still a daunting challenge. Organic metal chalcogenides (OMCs) are a type of newly emerging 2D materials, with metal chalcogenide layers covalently anchored by long‐range ordered organic functional motifs, these materials are extremely desirable but impossible to realize by traditional methods. Both the inorganic layer and organic functional motifs of OMCs are highly designable and thus provide this type of 2D materials with enormous variety in terms of their structure and properties. This Minireview aims to review the latest developments in OMCs and their bulk precursors. Firstly, the structure types of the bulk precursors for OMCs are introduced. Second, the synthesis and applications of OMC 2D materials in photoelectricity, catalysis, sensors, and energy transfer are explored. Finally, the challenges and perspectives for future research on OMCs are discussed. [ABSTRACT FROM AUTHOR]

The modification of inorganic two‐dimensional (2D) materials with organic functional motifs is in high demand for the optimization of their properties, but it is still a daunting challenge. Organic metal chalcogenides (OMCs) are a type of newly emerging 2D materials, with metal chalcogenide layers covalently anchored by long‐range ordered organic functional motifs, these materials are extremely desirable but impossible to realize by traditional methods. Both the inorganic layer and organic functional motifs of OMCs are highly designable and thus provide this type of 2D materials with enormous variety in terms of their structure and properties. This Minireview aims to review the latest developments in OMCs and their bulk precursors. Firstly, the structure types of the bulk precursors for OMCs are introduced. Second, the synthesis and applications of OMC 2D materials in photoelectricity, catalysis, sensors, and energy transfer are explored. Finally, the challenges and perspectives for future research on OMCs are discussed. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid superlattices (OIHSLs) hold attractive physical and chemical properties, while the construction of single‐crystal covalent OIHSLs has not been achieved. Herein a coordination assembly strategy was proposed to create a single‐crystal covalent OIHSL PbBDT (BDT=1,4‐benzenedithiolate), where layered [PbS2] sublattice covalently connects with benzene sublattice. The covalent bonding offers better thermo‐/chemi‐stability, inter‐sublattice electron transport, and unique organic‐group‐functionalized surface, which may enable better performances in chemical applications than non‐covalent OIHSL. These features endow PbBDT with the highest sensitivity, the lowest detection limit and excellent selectivity towards NO2 at room temperature among all chemiresistive gas‐sensing materials with reported response time less than 2 min without the need of light assistance. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid superlattices (OIHSLs) hold attractive physical and chemical properties, while the construction of single‐crystal covalent OIHSLs has not been achieved. Herein a coordination assembly strategy was proposed to create a single‐crystal covalent OIHSL PbBDT (BDT=1,4‐benzenedithiolate), where layered [PbS2] sublattice covalently connects with benzene sublattice. The covalent bonding offers better thermo‐/chemi‐stability, inter‐sublattice electron transport, and unique organic‐group‐functionalized surface, which may enable better performances in chemical applications than non‐covalent OIHSL. These features endow PbBDT with the highest sensitivity, the lowest detection limit and excellent selectivity towards NO2 at room temperature among all chemiresistive gas‐sensing materials with reported response time less than 2 min without the need of light assistance. [ABSTRACT FROM AUTHOR]

In response to ever‐increasing application requirements in lighting and displays, a tremendous emphasis is being placed on single‐component white‐light emission. Single‐component inorganic borates doped with rare earth metal ions have shown prominent achievements in white‐light emission. The first environmentally friendly defect‐induced white‐light emitting crystalline inorganic borate, Ba2[Sn(OH)6][B(OH)4]2, has been prepared. Additionally, it is the first borate‐stannate without a Sn−O−B linkage. Notably, Ba2[Sn(OH)6][B(OH)4]2 shows Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.42, 0.38), an ultrahigh color rendering index (CRI) of 94.1, and an appropriate correlated color temperature (CCT) of 3083 K. Such a promising material will provide a new approach in the development of white‐light emitting applications. [ABSTRACT FROM AUTHOR]

In response to ever‐increasing application requirements in lighting and displays, a tremendous emphasis is being placed on single‐component white‐light emission. Single‐component inorganic borates doped with rare earth metal ions have shown prominent achievements in white‐light emission. The first environmentally friendly defect‐induced white‐light emitting crystalline inorganic borate, Ba2[Sn(OH)6][B(OH)4]2, has been prepared. Additionally, it is the first borate‐stannate without a Sn−O−B linkage. Notably, Ba2[Sn(OH)6][B(OH)4]2 shows Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.42, 0.38), an ultrahigh color rendering index (CRI) of 94.1, and an appropriate correlated color temperature (CCT) of 3083 K. Such a promising material will provide a new approach in the development of white‐light emitting applications. [ABSTRACT FROM AUTHOR]

Superlattice materials offer new opportunities to modify optical and electrical properties of recently emerging 2D materials. The insertion of tetraethylbenzidine (EtDAB) into interlamination of the established 2D PbI2 semiconductor through a mild solution method yielded the first lead iodide superlattice, EtDAB⋅4PbI2 (EtDAB=tetraethylbenzidine), with radical and non‐radical forms. The non‐radical form has a non‐ionic structure that differs from the common ionic structures for inorganic–organic hybrid lead halides. The radical form shows five orders of magnitude greater conductance and broader photoconductive response range (UV/Vis → UV/Vis‐IR), than pure PbI2 and the non‐radical form of the superlattice. Lead the way: The first lead‐iodide superlattice constructed from non‐ionic organic molecules and PbI2 through van der Waals interactions is a new type of inorganic–organic hybrid and has a radical and a non‐radical form. The radical form has an almost five orders of magnitude greater conductivity and broader band photoconductive response than that of the non‐radical form or pure PbI2. [ABSTRACT FROM AUTHOR]

Superlattice materials offer new opportunities to modify optical and electrical properties of recently emerging 2D materials. The insertion of tetraethylbenzidine (EtDAB) into interlamination of the established 2D PbI2 semiconductor through a mild solution method yielded the first lead iodide superlattice, EtDAB⋅4PbI2 (EtDAB=tetraethylbenzidine), with radical and non‐radical forms. The non‐radical form has a non‐ionic structure that differs from the common ionic structures for inorganic–organic hybrid lead halides. The radical form shows five orders of magnitude greater conductance and broader photoconductive response range (UV/Vis → UV/Vis‐IR), than pure PbI2 and the non‐radical form of the superlattice. [ABSTRACT FROM AUTHOR]

Owing to the structural diversity and potential applications in optoelectronic devices, inorganic-organic hybrid materials have attracted extensive attentions in recent years. They are widely used in the fields of fluorescence, photoconductivity, ferroelectricity and solar cells. A new compound, [(Et 2 )HDABH(Et 2 )] 2 Pb 5 I 14 ·2H 2 O (DAB = benzidine), was solvothermally synthesized using [(Et 2 )HDABH(Et 2 )] 2+ as templates and balance cations. The structure is consisted of one-dimensional (1D) nanobelt iodoplumbate, [(Et 2 )HDABH(Et 2 )] 2+ dications and water molecules. The compound exhibits typical semiconductive behaviors, whose conductivity increases along with the raising of temperature. The compound also shows high electrical response to humidity, which indicates great potential application in humidity quantitatively detecting. [ABSTRACT FROM AUTHOR]

Electrically bistable materials have important applications in memory, displays, switches, sensors, and quantum computation. This communication reports a metal–organic framework (MOF) material as a new type of electrically bistable material. Taking advantage of the flexible structure of MOF materials, the electrically bistable states of the MOF were reversibly modulated between its crystalline and amorphous phases. Interestingly, the material's amorphous phase exhibited anomalously higher conductivity than the crystalline phase. Our results illustrated a convenient method to develop electrically bistable materials from MOFs. [ABSTRACT FROM AUTHOR]

Crystalline nanotube array would create great opportunity for novel electrical application. Herein we report the first example of a metal halide based crystalline nanotube array which is constructed from an unprecedented giant [PbII18I54(I2)9] wheel cluster, as determined by synchrotron Xray diffraction. The electrical properties of the single crystal were studied and the present compound shows typical semiconductivity and highly anisotropic conductivity. [ABSTRACT FROM AUTHOR]

Crystalline nanotube array would create great opportunity for novel electrical application. Herein we report the first example of a metal halide based crystalline nanotube array which is constructed from an unprecedented giant [PbII18I54(I2)9] wheel cluster, as determined by synchrotron Xray diffraction. The electrical properties of the single crystal were studied and the present compound shows typical semiconductivity and highly anisotropic conductivity. [ABSTRACT FROM AUTHOR]

The modification of inorganic two‐dimensional (2D) materials with organic functional motifs is in high demand for the optimization of their properties, but it is still a daunting challenge. Organic metal chalcogenides (OMCs) are a type of newly emerging 2D materials, with metal chalcogenide layers covalently anchored by long‐range ordered organic functional motifs, these materials are extremely desirable but impossible to realize by traditional methods. Both the inorganic layer and organic functional motifs of OMCs are highly designable and thus provide this type of 2D materials with enormous variety in terms of their structure and properties. This Minireview aims to review the latest developments in OMCs and their bulk precursors. Firstly, the structure types of the bulk precursors for OMCs are introduced. Second, the synthesis and applications of OMC 2D materials in photoelectricity, catalysis, sensors, and energy transfer are explored. Finally, the challenges and perspectives for future research on OMCs are discussed. [ABSTRACT FROM AUTHOR]

We investigate the impact of different derivatives of 1,4-diazabicyclo[2.2.2]octane on the crystal structures of iodoplumbates by systematically increasing the size of the same organic amine, and present two new 1-D iodoplumbates. Optical studies reveal the semiconductor characteristics of all as-synthesized iodoplumbate hybrids. [ABSTRACT FROM AUTHOR]

Two new different-bond-type hybrid compounds, (Hg6P4Cl3)(PbCl3) (1) and (Hg23P12)(ZnCl4)6 (2), with supramolecular interactions between host and guest moieties, which based on metal-pnicogen, pnicogen-pnicogen, and metal-halogen bonds were obtained by solid-state reactions. Compounds 1 and 2 show large second-harmonic-generation (SHG) activity and are transparent in the wide mid-IR region, providing an effective route for searching new IR nonlinear-optical material systems by combining two or more different bond types with no IR absorption within a single compound through supramolecular assembly. Theory predications based on first-principles calculations are also performed on the SHG properties of 1 and 2. [ABSTRACT FROM AUTHOR]

Abstract: Inorganic–organic hybrids with mixed halo atoms or organically coordinated halometal-complex cations are rare. A series` of haloplumbate hybrids with these structural features, [Cu(phen)2Cl] n (PbCl3) n (phen = 1,10-phenanthroline) (1), [Cu(phen)2Cl] n [PbClI(Cl0.5I0.5)] n (2), and [Cu(phen)2I] n (PbI3) n (3), have been solvothermally synthesized using phen coordinated halocopper(II) complexes as templates and balance cations. Their haloplumbate ions all show 1-D chain structures. Compounds 1–3 feature the hybridization of inorganic–organic hybrids: 1) their absorption edges fall in the range of those of semiconductors, which is typical for bulk lead(II) halides, but show a red shift compared with those of the latter; 2) bulk lead(II) halides are nonluminous upon UV irradiation, but introduction of the phen coordinated halocopper(II) complexes as templates enable the hybrids to emit blue light. Their luminescent intensities gradually decrease with the increase of I content, which indicates the potential to design and syntheses of new luminescent halide materials by means of variation of halo atoms and that iodoplumbates are not good candidates for luminescent materials. [Copyright &y& Elsevier]

Abstract: Two inorganic–organic hybrids, (MPDA)2n (Pb3I10) n (MPDA= p-Me3NC6H4NMe3) (1) and (H2EPDA) n (Pb2I6) n ·2nH2O (H2EPDA= p-Et2NHC6H4NHEt2) (2), have been solvothermally synthesized using p-phenylenediamine (PDA) as a precursor. Their iodoplumbate ions all show 1-D chain structures, but differ in interlinkage modes of [PbI6] octahedra: the former is both face- and edge-sharing, while the latter is face-sharing. The chain-like structure in 1 was reported only once in the literature. The results of optical absorption spectra and theoretical calculations for compounds PbI2 and 1–2 reveal a quantum confinement effect. Photoluminescent analyses show that they all exhibit blue emissions upon UV irradiation, which mainly originate from charge transfer from iodine atoms to ammoniums. [Copyright &y& Elsevier]

• Three novel inorganic-organic hybrid materials were synthesized. • Modulating the fluorescent emission by inserting neutral organic molecules. • Their photoluminescence exhibited yellow, red and orange light emission. Various luminescent organic-inorganic metal halide hybrid materials focus on fluorescence modulation. The commonly method to tunes the luminescence is usually via either modifying the structure of the inorganic anionic or the cation moiety. We here show the first time to modulate the fluorescent emission by inserting neutral organic molecules. The synthesis, crystal structure and optical properties of three organic-inorganic hybrids, [HEV][BiCl 5 (1), [MV] 3 [Bi 4 Cl 18 ·[C 16 H 10 (2) and [MV] 3 [Bi 4 Cl 18 ·[C 20 H 12 (3) ([HEV]2+ = N-proton-N′-ethyl-4,4′-bipyridinium, [MV]2+ = N,N′-dimethyl-4,4′-bipyridinium) were demonstrated. The compounds contain MV2+ cations, bismuth (III)-chloro anions and pyrene or perylene molecules achieve fluorescence modulation upon the insertion of neutral molecules. [ABSTRACT FROM AUTHOR]

The electronic conductivity (EC) of metal–organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2O on the EC of MOFs is rarely reported. We explored the effect of H2O on the EC in the MOFs (NH2)2‐MIL‐125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2SO4@(NH2)2‐MIL‐125 by H2O was observed. Brønsted acid–base pairs formed with the −NH2 groups, and H2SO4 played an important role in promoting the charge transfer from H2O to the MOF. Based on H2SO4@(NH2)2‐MIL‐125, a high‐performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2O can remarkably influence the EC of MOFs, but it also revealed that post‐modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high‐performance sensing materials. [ABSTRACT FROM AUTHOR]

The electronic conductivity (EC) of metal–organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2O on the EC of MOFs is rarely reported. We explored the effect of H2O on the EC in the MOFs (NH2)2‐MIL‐125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2SO4@(NH2)2‐MIL‐125 by H2O was observed. Brønsted acid–base pairs formed with the −NH2 groups, and H2SO4 played an important role in promoting the charge transfer from H2O to the MOF. Based on H2SO4@(NH2)2‐MIL‐125, a high‐performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2O can remarkably influence the EC of MOFs, but it also revealed that post‐modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high‐performance sensing materials. [ABSTRACT FROM AUTHOR]

The first example of a metal-halide-based crystalline nanotube array, (Pr2DABCO)21 [Pb18I54(I2)9] [Pb2I9] 2I5·13H2O is prepared by solvothermal reaction ofPbI2, DABCO, conc. [ABSTRACT FROM AUTHOR]

Pore size plays a critical role in determining the performance of metal‐organic frameworks (MOFs) in catalysis, sensing, and gas storage or separation. However, revealing the pore‐size/property relationship remains extremely challenging because ideal structure models possessing different pore sizes but having the same components are lacking. In this work, a solvent‐coordination directed structure swelling method was developed for modulating the ratio between the large and narrow pore phases of a flexible MOF, MIL‐88B. Pore‐size‐dependent gas sensitivity and selectivity were studied for the first time in the MIL‐88B samples. The optimized MIL‐88B‐20 % sample showed one of the best sensing performances among all the reported MOF‐based H2S‐sensing materials. This work not only provides a method to synthesize ideal structure models for revealing the relationship between pore‐size and properties, but also may inspire the development of high‐performance gas sensing materials. [ABSTRACT FROM AUTHOR]

Pore size plays a critical role in determining the performance of metal‐organic frameworks (MOFs) in catalysis, sensing, and gas storage or separation. However, revealing the pore‐size/property relationship remains extremely challenging because ideal structure models possessing different pore sizes but having the same components are lacking. In this work, a solvent‐coordination directed structure swelling method was developed for modulating the ratio between the large and narrow pore phases of a flexible MOF, MIL‐88B. Pore‐size‐dependent gas sensitivity and selectivity were studied for the first time in the MIL‐88B samples. The optimized MIL‐88B‐20 % sample showed one of the best sensing performances among all the reported MOF‐based H2S‐sensing materials. This work not only provides a method to synthesize ideal structure models for revealing the relationship between pore‐size and properties, but also may inspire the development of high‐performance gas sensing materials. [ABSTRACT FROM AUTHOR]

(Hg6P4Cl3)(PbCl3) (I) and (Hg23P12)(ZnCl4)6 (II) are synthesized by solid state reactions of Hg2Cl2, Hg(CN)2, PbCl2, and red phosphorus for compound (I) (Pyrex tube, 340 °C, 5 d, 90% yield), and from mixtures of HgCl2, Hg2Cl2, Zn, and red phosphorus for compound (II) (Pyrex tube, 400 °C, 5 d, 80% yield). [ABSTRACT FROM AUTHOR]

Accurate fire warning is very important for people's life and property safety. The most commonly used fire alarm is based on the detection of a single factor of gases, smoke particles, or temperature, which easily causes false alarm due to complex environmental conditions. A facile multi‐factor route for fabricating an accurate analog fire alarm using a Pb5S2I6 nanowire mesh based on its photoelectric and gas‐sensing dual function is presented. The Pb5S2I6 nanowire mesh presents excellent photoelectric detection capabilities and is sensitive to ppm‐level NO2 at room temperature. Under the "two‐step verification" circuit of light and gas factors, the bimodal simulation fire alarm based on this Pb5S2I6 nanowire mesh can resist the interference of complex environmental factors and effectively reduce the false alarm rate. [ABSTRACT FROM AUTHOR]

A novel open-framework cadmium selenite bromide, [Cd10(SeO3)8Br4]·HBr·H2O (1), has been obtained by a solid-state reaction at 450°C, and the structure has been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in Pbcm of the orthorhombic system: a=10.882(3), b=16.275(5), c=18.728(6)Å, V=3317(2)Å3, R1/wR2=0.0411/0.0659. Compound 1 is characteristic of a novel 3-D open-framework structure, composing ∞ 2[CdSeO3] layers and the pillars of edge-shared CdO3Br2 square pyramids. The lattice water molecules and the HBr molecules locate in the voids of the framework. Optical absorption spectrum of 1 reveals the presence of an optical gap of 1.65eV. Solid-state photoluminescent study indicates that compound 1 exhibits strong violet emission. TG–DSC measurement shows that compound 1 is thermally stable up to 200°C. [ABSTRACT FROM AUTHOR]

High‐quality MOF thin films with high orientation and controlled thickness are extremely desired for applications. However, they have been only successfully fabricated on flat substrates. Those MOF 2D thin films are limited by low exposed area and slow mass transport. To overcome these issues, MOF 3D thin films with good crystallinity, preferred orientation, and precisely controllable thickness in nanoscale were successfully prepared in a controllable layer‐by‐layer manner on nanowire array substrate for the first time. The as‐prepared Cu‐HHTP 3D thin film is superior to corresponding 2D thin films and showed one of the highest sensitivity, lowest LOD, and fastest response among all reported chemiresistive NH3 sensing materials at RT. This work provides a feasible approach to grow preferred‐oriented 3D MOF thin film, offering new perspectives for constructing MOF‐based heterostructures for advanced applications. [ABSTRACT FROM AUTHOR]

High‐quality MOF thin films with high orientation and controlled thickness are extremely desired for applications. However, they have been only successfully fabricated on flat substrates. Those MOF 2D thin films are limited by low exposed area and slow mass transport. To overcome these issues, MOF 3D thin films with good crystallinity, preferred orientation, and precisely controllable thickness in nanoscale were successfully prepared in a controllable layer‐by‐layer manner on nanowire array substrate for the first time. The as‐prepared Cu‐HHTP 3D thin film is superior to corresponding 2D thin films and showed one of the highest sensitivity, lowest LOD, and fastest response among all reported chemiresistive NH3 sensing materials at RT. This work provides a feasible approach to grow preferred‐oriented 3D MOF thin film, offering new perspectives for constructing MOF‐based heterostructures for advanced applications. [ABSTRACT FROM AUTHOR]

The coordination of copper(I) halide moiety and sulfur-donor ligand to construct copper-halide-sulfur complex is proposed to combine the prominent optical and electronic functions from both copper halide and copper chalcogenide moieties. However, currently reported copper-halide-sulfur complexes mostly possess low dimensional structure or lack continuous electron transportation, thereby being unfavorable for electrical-based application. Herein, we report an unprecedented copper (I) complex {(pt) 2 Cu 3 I 3 } n (denoted as UJN-Cu6 , pt = pyridin-1-ium-4-thiolate), which contains the first reported three-dimensional (3D) copper-halide-sulfur semiconductive framework. UJN-Cu6 was constructed by a deliberately synthesis strategy, where the copper iodine species were monodentate bridged by the sulfur-donor ligand, which is different from the most reported multidentate coordination mode. The thin film device of UJN-Cu6 can detect both UV and visible light with high switching on/off ratios and excellent photocurrent reproducibility. Further, the thin film device exhibits good sensitivity, short response time and high selectivity toward detecting hazardous NO 2 /N 2 O 4. Mechanism studies indicate that the semiconductive copper-halide-sulfur skeleton contributes a lot to the electrical-based detection applications. The functional –N–H groups hanging on the surface of channel bring about highly selective recognition of NO 2 /N 2 O 4 molecules. [Display omitted] • The first 3D copper-halide-sulfur semiconductive framework was prepared via a well-designed synthesis strategy. • Functional organic pyridines hanging on the inorganic semiconductive skeleton affords fascinating electrical detections. • Detecting both UV and visible light with high switching on/off ratios and excellent photocurrent reproducibility. • Detecting hazardous NO 2 with good sensitivity, short response time and high selectivity. • Experimental and theoretical technologies were employed to disclose the difunctional detection mechanism. [ABSTRACT FROM AUTHOR]

Arranging ionic liquids (ILs) with long‐range order can not only enhance their performance in a desired application, but can also help elucidate the vital between structure and properties. However, this is still a challenge and no example has been reported to date. Herein, we report a feasible strategy to achieve a crystalline IL via coordination self‐assembly based reticular chemistry. IL1MOF, was prepared by designing an IL bridging ligand and then connecting them with metal clusters. IL1MOF has a unique structure, where the IL ligands are arranged on a long‐range ordered framework but have a labile ionic center. This structure enables IL1MOF to break through the typical limitation where the solid ILs have lower proton conductivity than their counterpart bulk ILs. IL1MOF shows 2–4 orders of magnitude higher proton conductivity than its counterpart IL monomer across a wide temperature range. Moreover, by confining the IL within ultramicropores (<1 nm), IL1MOF suppresses the liquid–solid phase transition temperatures to lower than −150 °C, allowing it to function with high conductivity in a subzero temperature range. [ABSTRACT FROM AUTHOR]

Arranging ionic liquids (ILs) with long‐range order can not only enhance their performance in a desired application, but can also help elucidate the vital between structure and properties. However, this is still a challenge and no example has been reported to date. Herein, we report a feasible strategy to achieve a crystalline IL via coordination self‐assembly based reticular chemistry. IL1MOF, was prepared by designing an IL bridging ligand and then connecting them with metal clusters. IL1MOF has a unique structure, where the IL ligands are arranged on a long‐range ordered framework but have a labile ionic center. This structure enables IL1MOF to break through the typical limitation where the solid ILs have lower proton conductivity than their counterpart bulk ILs. IL1MOF shows 2–4 orders of magnitude higher proton conductivity than its counterpart IL monomer across a wide temperature range. Moreover, by confining the IL within ultramicropores (<1 nm), IL1MOF suppresses the liquid–solid phase transition temperatures to lower than −150 °C, allowing it to function with high conductivity in a subzero temperature range. [ABSTRACT FROM AUTHOR]

Heterostructured metal—organic framework (MOF)‐on‐MOF thin films have the potential to cascade the various properties of different MOF layers in a sequence to produce functions that cannot be achieved by single MOF layers. An integration method that relies on van der Waals interactions, and which overcomes the lattice‐matching limits of reported methods, has been developed. The method deposits molecular sieving Cu‐TCPP (TCPP=5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin) layers onto semiconductive Cu‐HHTP (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene) layers to obtain highly oriented MOF‐on‐MOF thin films. For the first time, the properties in different MOF layers were cascaded in sequence to synergistically produce an enhanced device function. Cu‐TCPP‐on‐Cu‐HHTP demonstrated excellent selectivity and the highest response to benzene of the reported recoverable chemiresistive sensing materials that are active at room temperature. This method allows integration of MOFs with cascading properties into advanced functional materials. [ABSTRACT FROM AUTHOR]

Heterostructured metal—organic framework (MOF)‐on‐MOF thin films have the potential to cascade the various properties of different MOF layers in a sequence to produce functions that cannot be achieved by single MOF layers. An integration method that relies on van der Waals interactions, and which overcomes the lattice‐matching limits of reported methods, has been developed. The method deposits molecular sieving Cu‐TCPP (TCPP=5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin) layers onto semiconductive Cu‐HHTP (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene) layers to obtain highly oriented MOF‐on‐MOF thin films. For the first time, the properties in different MOF layers were cascaded in sequence to synergistically produce an enhanced device function. Cu‐TCPP‐on‐Cu‐HHTP demonstrated excellent selectivity and the highest response to benzene of the reported recoverable chemiresistive sensing materials that are active at room temperature. This method allows integration of MOFs with cascading properties into advanced functional materials. [ABSTRACT FROM AUTHOR]

A new series of 2D catalytic materials whose inorganic surfaces are fully covered with pre-designed "promoter" groups are reported. One of them showed excellent biomimetic catalytic activity and provided the lowest detection limit to glucose among the reported 2D materials and their composite materials. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) are a kind of functional porous materials with the potential applications in gas adsorption and separation, catalysis, energy storage, sensor, and electrical conductivity. However, the insulating nature of the mostly MOFs limits their application in the electronic field. A new three-dimensional (3D) metal-organic framework composed of Cu2+ centres and polyacid linkers (TATAB3−) was synthesized by solvothermal method, which contains two types of Cu 24 cages. The crystal structure is cubic and each Cu is coordinated by five oxygen atoms which can be confirmed by the single crystal X-ray diffraction, infrared spectra and TGA analysis. The conductivity for this 3D MOF is increased by four orders of magnitude after doping with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and realizes the transformation from an insulator to semiconductor. A new three dimensional metal-organic frameworks composed of Cu2+ centres and polyacid linkers (TATAB3−) was synthesized by solvothermal method, which contains two types of Cu 24 cages. The conductivity of the Cu-MOF was increased by 4 orders of magnitude after doping with TCNQ molecules. This method realized the transformation of Cu-MOF from insulator to semiconductor. Finally, the Conductive mechanism of the doped Cu-MOF has been studied. Unlabelled Image • A new three dimensional metal-organic frameworks composed of Cu2+ centres and polyacid linkers (TATAB3-) was synthesized by solvothermal method, which contains two types of Cu 24 cages. • The structure of the as-synthesized Cu-MOF was not changed after doping with TCNQ molecules. • The conductivity of this 3D MOF was increased by four orders of magnitude after doping with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and realized the transformation from insulator to semiconductor. [ABSTRACT FROM AUTHOR]

Abstract Owing to the structural diversity and potential applications in optoelectronic devices, inorganic-organic hybrid materials have attracted great attentions in recent years. They have potential applications in the fields of fluorescence, photoconductivity, ferroelectricity and solar cells. A new inorganic-organic hybrid, [H 2 (dmen)]PbCl 4 (dmen = N , N -Dimethylethylenediamine), was solvothermally synthesized using [H 2 (dmen)]2+ as templates and balance cations. The inorganic structure is two-dimensional (2D) single layer perovskite. This compound exhibits typical semiconductive behavior, whose conductivity increases along with the raising of temperature. The compound also shows yellow light emission property, which indicates great potential application in light-emitting diodes. Graphical abstract A new compound, [H 2 (dmen)]PbCl 4 (dmen = N , N -Dimethylethylenediamine), has been solvothermally synthesized. The inorganic structure is two-dimensional (2D) single layer perovskite. This compound exhibits typical semiconductive behavior, whose conductivity increases along with the raising of temperature. The compound also shows yellow light emission property, which indicates great potential application in light-emitting diodes. Unlabelled Image Highlights • A new lead chloride hybrid, [H 2 (dmen)]PbCl 4 , was obtained by solvothermal method. • [H 2 (dmen)]PbCl 4 exhibits two-dimensional (2D) single layer perovskite structure. • [H 2 (dmen)]PbCl 4 exhibits typical semiconductive behavior. • [H 2 (dmen)]PbCl 4 shows yellow light emission property. [ABSTRACT FROM AUTHOR]

In this paper, two new 1-dimensional edge-shared organic–inorganic metal halide hybrids are reported. The sensitivity to nitrogen dioxide of [(Et) 2 MP]PbBr 3 is dramatically enhanced when the bromine is converted to iodine. [Display omitted] • Two new one-dimensional organic–inorganic metal halide hybrids were synthesized. • The compounds with excellent water stability and semiconducting properties. • A strategy of halogen modulation achieves a dramatic increase in NO 2 sensitivity. Organic-inorganic metal halide hybrids show great potential for applications in catalysis, solar cells, gas sensing, etc. Due to the highly designable structure, a novel strategy could be developed to improve their gas sensitivity in gas detection. Two new organic–inorganic metal halide hybrids have been synthesized using [(Et) 2 MP]+ (MP = p -mercaptopyridine, Et = ethyl) as the cationic template. The 1-dimensional inorganic chain provides good electron transport channels, and the electronic structure can be easily adjusted by changing the halogen to enhance the sensitivity of gas sensing. The difference in response values for NO 2 can reach 27 times before and after the halogen change. This work provides insight into the design of gas-sensing materials with improved properties. [ABSTRACT FROM AUTHOR]

Broad absorption, long-lived photogenerated carriers, high conductance, and high stability are all required for a light absorber toward its real application on solar cells. Inorganic-organic hybrid lead-halide materials have shown tremendous potential for applications in solar cells. This work offers a new design strategy to improve the absorption range, conductance, photoconductance, and stability of these materials. We synthesized a new photochromic lead-chloride semiconductor by incorporating a photoactive viologen zwitterion into a lead-chloride system in the coordinating mode. This semiconductor has a novel inorganic-organic hybrid structure, where 1-D semiconducting inorganic lead-chloride nanoribbons covalently bond to 1-D semiconducting organic π-aggregates. It shows high stability against light, heat, and moisture. After photoinduced electron transfer (PIET), it yields a long-lived charge-separated state with a broad absorption band covering the 200-900 nm region while increasing its conductance and photoconductance. This work is the first to modify the photoconductance of semiconductors by PIET. The observed increasing times of conductivity reached 3 orders of magnitude, which represents a record for photoswitchable semiconductors. The increasing photocurrent comes mainly from the semiconducting organic π-aggregates, which indicates a chance to improve the photocurrent by modifying the organic component. These findings contribute to the exploration of light absorbers for solar cells. [ABSTRACT FROM AUTHOR]

Single crystals of BaGeOSe2 are prepared by solid state reaction of a stoichiometric mixture of GeO2, Ba, Se, and extra KI as a flux (evacuated quartz tubes, 1. [ABSTRACT FROM AUTHOR]

A room-temperature solution phase reaction was developed to synthesize a covalent organic framework (COF) for the first time. The synthesized azodioxy-linked porphyrin-based COF (POR-COF) possesses a 2D chess board-like structure in the ab-plane and a 1D channel with an open-window size of around 1.9 nm along the c-axis in the modeled crystal structure. The electrical conductivity of POR-COF increases by more than 3 orders of magnitude through I2 doping. The photoconductivity of the I2-doped COF material was also studied firstly. POR-COF shows interesting doping-enhanced photo-current generation. [ABSTRACT FROM AUTHOR]

This paper synthesized six low-dimensional organic-inorganic hybrid metal halides by a solvothermal synthesis method in a methanol solution environment. This series of compounds exhibit broadband emission covering the entire visible spectra, with significant Stokes shift and long luminescence lifetime, and shows a tunable optical band gap ranging from 2.39 to 3.36 eV. [Display omitted] • Six new low-dimensional hybrid halides were synthesized by a solvothermal method. • This series of compounds exhibit broadband emissions covering the visible light range. • This series of compounds exhibit wide-bandgap tunability from 2.39 to 3.36 eV. In recent years, low-dimensional organic-inorganic metal halides have been widely used in photoluminescent diodes, solar cells, lasers, photodetectors, and other fields because of their rich structures and excellent optoelectronic properties. In this paper, organic cations H 2 DAB (DAB = benzidine) and H 2 TMB (TMB = 3, 3′, 5, 5′-tetramethylbenzidine) are used as structural templates and cations to regulate the structure of inorganic anions (0D, 1D) and then regulate the luminescence properties of the materials. Among them, the materials with one-dimensional inorganic structures show typical semiconductor behavior, and their electrical conductivity increases with the increase of temperature. The inorganic part of this series of compounds has large structural distortion, large bandgap, significant Stokes shift, and wideband emissions. It has a long fluorescence lifetime, ranging from nanosecond to millisecond. More interestingly, they realize the controllable adjustment of the colour of fluorescent light emitted from yellow-green light, yellow light, orange-red light to near-white light. This work provides a new structure model for understanding the structure-activity relationship between structure and luminescence properties. [ABSTRACT FROM AUTHOR]

A new 1D hybrid lead halide (dbod)Pb 2 Br 6 was synthesized by solvothermal method with 1,4-Diazoniabicyclo[2.2.2]octane, 1,4-dipropy2+ ((dobd)2+) as organic spacer and counter cation. [PbBr5] pyramids in the structure connects with each other through corner-sharing to constitute continuous [Pb 2 Br 6 ]2+ chains. The compound shows broad band orange emission under UV excitation and good conductivity at room-temperature. The material system hold potential for the application of white-light emitting diodes. [Display omitted] • A new 1D corner-shared hybrid lead bromide was synthesized by solvothermal method. • The compound exhibits broad band orange emission under UV excitation. • This compound shows a good conductivity at room- temperature. Hybrid metal halides with high chemistry versatility and electronic tunability is a promising material system for new-generation lighting and displaying. Lowing the dimensionality of inorganic moieties gives rise to the broad-band white emission of those materials. Here a new 1D hybrid lead bromide (dbod)Pb 2 Br 6 (dbod2+=1,4-Diazoniabicyclo[2.2.2]octane, 1,4-dipropy2+) was synthesized using organic dbod2+ as the spacer and balance cation. The compound showed a very broad emission with a full width half-maximum of 244 nm. With good electron conductivity, this series of compounds hold potential for the application of white-light LEDs. [ABSTRACT FROM AUTHOR]

A new 1D inorganic–organic hybrid [(Me 3)DAB(Me 3)]PbI 4 ·H 2 O (DAB = benzidine) with perovskite-like structure was synthesized by solvothermal method, which is consisted by 1D inorganic PbI 4 - anion chains and [(Me 3)DAB(Me 3)]2+ dications. Four [(Me 3)DAB(Me 3)]2+ cation cleverly encapsulated the folded and extended 1D chain to form a square channel. This compound can maintain high stability in various solvents and exhibit typical semiconductor behavior. In addition, this compound shows a response of 5 orders magnitude high at 100% RH. [Display omitted] • A new 1D perovskite-like material was synthesized by solvothermal method. • This compound has good chemical stability to various solvents. • This compound has a current response of 5 orders of magnitude high at 100% RH. Inorganic-Organic hybrid perovskite-like materials have potential application in photodetection, sensor and solar cells etc. However, these materials still face the challenge of poor stability. A new inorganic–organic hybrid material was synthesized by solvothermal method using H 2 DAB as the template and counter cation. The structure is composed of one-dimensional (1D) inorganic perovskite-like chain, [(Me 3)DAB(Me 3)]2+ (DAB = benzidine) dications and water molecules. This compound exhibits good stability to water and organic solvents, and shows typical semiconductor behavior. Interestingly, the compound also shows great potential for humidity sensing, including linear sensitivity (10–100%), high response (5 orders of magnitude of current change), and fast recovery time. [ABSTRACT FROM AUTHOR]

Innenrücktitelbild: Van der Waals Heterostructured MOF-on-MOF Thin Films: Cascading Functionality to Realize Advanced Chemiresistive Sensing (Angew. Der MOF-auf-MOF-Dünnfilm zeigt das stärkste Ansprechverhalten auf Benzol, das bisher für regenerierbare chemoresistive Sensormaterialien bei Raumtemperatur berichtet wurde. Gas-Sensoren, Heterostrukturen, MOF-auf-MOF, Dünne Schichten, Van-der-Waals-Grenzflächen. [Extracted from the article]