The development of low-dimensional perovskite micro/nanostructures with high water stability for novel photonic/electronic applications is highly desirable. Herein, one-dimensional (1D) ...organic-inorganic hybrid perovskite micro-belts (AD)Pb
2
Cl
5
(OIHP-AD, AD = acridine) were facilely synthesized through fast precipitation in aqueous solution at room temperature without any organic solvent and expensive alkyl halide. Luminescent properties and water stability are efficiently enhanced due to the highly regular arrangement of the protonated AD dyes with larger steric hindrance distributed in the perovskite host-guest system, which can afford denser crystal packing to prevent water erosion. The OIHP-AD micro-belts present upconversion fluorescence, polarized photoemission and optical waveguide performances with a low loss coefficient (0.004 dB μm
−1
) during propagation, thus extending the applications of 1D perovskite micro/nanostructures to potential optical communication micro-devices.
The development of low-dimensional perovskite micro/nanostructures with high water stability for novel photonic/electronic applications is highly desirable.
Embedding cubane M4(OH)4 (M=Ni, Co) clusters within the matrix of metal–organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material ...type based on the pore‐space partition of the cubic primitive minimal‐surface net (MOF‐14‐type) has been realized. CTGU‐15 made from the Ni4(OH)4 cluster not only has very high BET surface area (3537 m2 g−1), but also exhibits bi‐microporous features with well‐defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU‐15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU‐15 (1:2) made from ketjen black (KB) and CTGU‐15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at low potential (0.6 V). The isostructural cobalt structure (CTGU‐16) has also been synthesized, further expanding the application potential of this material type.
Split pores: A new 3D microporous metal–organic framework containing cubane Ni4(OH)4 clusters can serve as an electrocatalyst for the methanol oxidation reaction (MOR). The optimal hybrid material shows impressive electrocatalytic performance including a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at a very low potential (0.6 V).
The formation of high‐nuclearity silver(I) clusters remains elusive and their potential applications are still underdeveloped. Herein, we firstly prepared a chain‐like thiolated AgI complex ...{Ag18(StBu)10(NO3)8(CH3CN)2(H2O)2 ⋅ Ag18(StBu)10(NO3)8(CH3CN)6}n (abbreviated as Ag18) in which two similar Ag18 clusters are assembled by NO3− anions. The solution containing Ag18 reacted with hydrogen sulfide with controlled concentration, promptly producing another identifiable and bright red‐emitting high‐nuclearity silver(I) cluster, Ag62(S)13(StBu)32(NO3)4 (abbreviated as Ag62). We tracked the transformation using time‐dependent electrospray ionization mass spectrometry (ESI‐MS), UV/Vis absorption and photoluminescence spectra. Based on this cluster transformation, we further developed an ultra‐sensitive turn‐on sensor detecting H2S gas with an ultrafast response time (30 s) at a low detection limit (0.13 ppm). This work opens a new way of understanding the growth of metal clusters and developing their luminescent sensing applications.
Two similar Ag18 clusters are assembled via NO3− anions to form a chain‐like thiolated AgI complex (abbreviated as Ag18). The solution containing Ag18 reacted with H2S with controlled concentration, promptly producing another identifiable and bright red‐emitting high‐nuclearity silver(I) cluster Ag62. Based on this cluster transformation, an ultra‐sensitive turn‐on sensor was developed to the detection of H2S gas with an ultrafast response time (30 s) at a low concentration (0.13 ppm).
Intricately interwoven topologies are continually being synthesized and are ultimately equally versatile and significant at the nanoscale level; however, reports concerning ravel structures, which ...are highly entwined new topological species, are extremely rare and fraught with tremendous synthesis challenges. To solve the synthesis problem, a tetrapodontic pyridine ligand L1 with two types of olefinic bond units and two Cp*M‐based building blocks (E1, M=Rh; E2, M=Ir) featuring large conjugated planes was prepared to perform the self‐assembly. Two unprecedented 5+10 icosanuclear molecular 4‐ravels containing four crossings were obtained by parallel‐displaced π⋅⋅⋅π interactions in a single‐step strategy. Remarkably, reversible structural transformations between the 4‐ravel and the corresponding metallocage could be realized by concentration changes and solvent‐ and guest‐induced effects. X‐ray crystallographic data and NMR spectroscopy provide full confirmation of these phenomena.
Two unprecedented 5+10 icosanuclear molecular 4‐ravels containing four crossings have been generated using a single‐step strategy. This topology is achieved by utilizing parallel‐displaced π⋅⋅⋅π interactions with carefully selected naphthoquinoyl Cp*M building blocks and X‐shaped pyridyl ligands.
The development of efficient enzyme immobilization to promote their recyclability and activity is highly desirable. Zeolitic imidazolate framework‐8 (ZIF‐8) has been proved to be an effective ...platform for enzyme immobilization due to its easy preparation and biocompatibility. However, the intrinsic hydrophobic characteristic hinders its further development in this filed. Herein, a facile synthesis approach was developed to immobilize pepsin (PEP) on the ZIF‐8 carrier by using Ni2+ ions as anchor (ZIF‐8@PEP‐Ni). By contrast, the direct coating of PEP on the surface of ZIF‐8 (ZIF‐8@PEP) generated significant conformational changes. Electrochemical oxygen evolution reaction (OER) was employed to study the catalytic activity of immobilized PEP. The ZIF‐8@PEP‐Ni composite attains remarkable OER performance with an ultralow overpotential of only 127 mV at 10 mA cm−2, which is much lower than the 690 and 919 mV overpotential values of ZIF‐8@PEP and PEP, respectively.
A facile synthesis approach was developed to immobilize enzyme on the ZIF‐8 carrier by using Ni2+ ions as anchor, which can significantly promote the recyclability and activity of the enzyme.
This review mainly focuses on introducing the different assembled strategies of the heterometallic-organic frameworks (HMOFs), and highlights the influence of the synergistic effect on their enhanced ...physical and chemical performances.
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•The recent advances are carefully introduced for the functional heterometallic-organic frameworks (HMOFs) in detail.•The assembled strategies are presented to isolate the functional HMOFs, such as such as one-pot synthesis, post-synthetic modification, ion exchange strategy, and grinding method, etc.•This work shows the enhanced performances of HMOFs via the synergistic effect for the adsorption, catalysis, magnetism, and fluorescence, etc.•The conclusion and outlook are given for the future development of HMOF materials.•This review will supply some useful guides for the preparation of new HMOF materials for wide applications in the whole energy landscape.
Metal-organic frameworks (MOFs) have different structures and various intrinsic properties, such as large specific surface area, flexible and adjustable structural configurations, coordinately-unsaturated metal center, etc., which facilitate the rapid development and wide application of coordination chemistry, over the past decades, including gas adsorption, catalysis, and magnetism. Although the metals in various regions of the periodic table have been explored to build different monometallic MOFs, the researches about functional heterometallic-organic framework (HMOF) materials have not been particularly in-depth. Compared with monometallic MOFs, some special positions are occupied by the heterogeneous metals in one HMOF, which will result in interesting network topologies, and the excellent synergistic effect between the different metal ions will make the physical and chemical properties to be effectively enhanced. This review mainly focuses on introducing the latest progresses of HMOFs, including the various synthesis strategies, applications and outlooks, which may provide some useful guidance for the preparation of novel HMOF materials and make them widely used in the whole energy landscape.
An alkali-resistant Zn-MOF directed by BMIBr ionic liquid, (BMI)
2
Zn
3
(ptptc)
2
(
1
), based on a π-electron-rich terphenyl-tetracarboxylic acid, has been synthesized under the combination of ...hydro/solvothermal and ionothermal condition (BMI = 1-butyl-3-methylimidazolium, H
4
ptptc =
p
-terphenyl-3,3′′,5,5′′-tetracarboxylic acid). In
1
, the trinuclear Zn(
ii
) clusters are linked by the organic moieties of the ptptc ligands, resulting in a 3D anionic framework structure with highly disordered BMI
+
cations filled in the pores.
1
exhibits good chemical stability in water and NaOH solutions (pH range of 7-12), which allow it to detect antibiotics and nitroaromatic explosives in an aquatic system.
1
represents high fluorescence quenching efficiency toward NFs (furazolidone, FZD; nitrofurazone, NZF; nitrofurantoin, NFT), NMs (ronidazole, RDZ; metronidazole, MDZ; dimetridazole, DTZ; ornidazole, ODZ) and nitrophenol (2-nitrophenol, 2-NP; 3-nitrophenol, 3-NP; 4-nitrophenol, 4-NP; 2,4,6-trinitrophenol, TNP) in water solution, respectively.
An alkali-resistant 3D anionic Zn-MOF directed by BMIBr ionic liquid has been synthesized for aqueous-phase detection of antibiotics and nitroaromatic explosives.
Molecular cocrystals have received much attention for tuning physicochemical properties in pharmaceutics, luminescence, organic electronics, and so on. However, the effective methods for the ...formation of orderly cocrystal thin films are still rather limited, which have largely restricted their photofunctional and optoelectronic applications. In this work, a fast crystallization-deposition procedure is put forward to obtain acridine (AD)-based cocrystals, which are self-assembled with three typical isophthalic acid derivatives (IPA, IPB, and TMA). The obtained donor–acceptor cocrystal complexes exhibit an adjustable energy level, wide range of photoluminescence color, and rotational angle-dependent polarized emission. The orderly and uniform cocrystal thin films further present tunable one-/two-photon up-conversion and different semiconductor properties. Particularly, AD-TMA cocrystal thin film shows a rare example of a molecule level heterojunction with the alternating arrangement of AD electronic acceptor layers and TMA electronic donor layers, and thus, provides a way for efficient mobility and separation of electron–hole pairs. A large on–off photocurrent ratio of more than 104 can be achieved for the AD-TMA thin film, which is higher than state-of-the-art molecular semiconductor systems. Therefore, this work extends the application scopes of orderly cocrystal thin film materials for future luminescent and optoelectronic micro-/nanodevices.
Two novel compounds, a molecular trefoil knot and a Solomon link, were constructed successfully through the cooperation of multiple π-π stacking interactions. A reversible transformation between the ...trefoil knot and the corresponding 2 + 2 macrocycle could be achieved by solvent- and guest-induced effects. However, the Solomon link maintains its stability in different concentrations, solvents and guest molecules. Single-crystal X-ray crystallographic data, NMR spectroscopic experiments and ESI-MS support the synthesis and structural assignments. These synthesis methods open the door to the further development of smart materials, which will push the advancement of rational design of biomaterials.
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