Correction: A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion.

Correction for 'A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion' by Xuze Pan, et al., Dalton Trans., 2023, 52, 3896-3906, https://doi.org/10.1039/D2DT03158B.

AIEE-active dichlorobenzene and chlorobenzene ratiometric fluorescent probe based on [2.2]paracyclophane.

Two AIEE-active [2.2]paracyclophanyl-based diester and monoester (1a and 1b) were facilely synthesized by one-pot method and applied as ratiometric fluorescent probe to detect dichlorobenzene (DCB) and chlorobenzene (CB). Compared with compound 1b, 1a exhibits high sensitivity and low detection limits for DCB and CB in dichloromethane (DCM), particularly, the detection sensitivities for ortho-dichlorobenzene (o-DCB), meta-dichlorobenzene (m-DCB) and chlorobenzene can be modulated by AIEE behavior with lower detection limits of 23.64, 56.27, and 5.92 ppm, respectively in THF/H2O mixed solutions with water fraction (fw) of 70 % due to the formation of aggregation-state. The X-ray structure analysis, theoretical calculations and photophysical properties in different solvents were investigated to reveal the distinctive photophysical behaviors of 1a and 1b. The facile synthesis, X-ray structure, AIEE modulated sensing properties for o-DCB, m-DCB, and CB in DCM and THF/H2O mixed solutions make 1a potential application as fluorescent probe for trace DCB and CB detection in drinking water.

Highly bifunctional Rh2P on N,P-codoped carbon for hydrazine oxidation assisted energy-saving hydrogen production.

Highly pure Rh2P nanoparticles on N,P-codoped carbon were synthesized by a simple "mix-and-pyrolyze" method using one kind of low-cost nucleotide as the carbon, nitrogen and phosphorus source, which exhibits excellent bifunctional activity for the hydrogen reduction and hydrazine oxidation reactions, achieving energy-efficient hydrogen production.

RhIII-Catalyzed Direct Heteroarylation of Unactivated C(sp3)-H with N-Heteroaryl Boronates.

Disclosed herein is a rhodium(III)-catalyzed direct heteroarylation reaction between unactivated aliphatic C(sp3)-H bonds in 2-alkylpyridines and heteroaryl organoboron reagents. This catalytic protocol is compatible with various heterocyclic boronates containing ortho- and meta-pyridine, pyrazoles, furan, and quinoline with strong coordination capability. The achievement of this methodology provides an efficient route to build new C(sp3)-heteroaryl bonds.

A Porous Carbazolic Al-MOF for Efficient Aerobic Photo-Oxidation of Sulfides into Sulfoxides under Air.

A robust, microporous, and photoactive aluminum-based metal-organic framework (Al-MOF, LCU-600) has been assembled by an in situ-formed [Al3O(CO2)6] trinuclear building unit and a tritopic carbazole ligand. LCU-600 shows a high water stability and permanent porosity for N2 and CO2 adsorption. Notably, the incorporation of photoresponsive carbazole moieties into LCU-600 makes it a highly efficient and recyclable photocatalyst for aerobic photo-oxidation of sulfides into sulfoxides under an air atmosphere at room temperature. Mechanism investigations unveil that photogenerated holes (h+), superoxide radical anion (O2•-), and singlet oxygen (1O2) are critical active spices for the photo-oxidation reaction performed in an air atmosphere.

A porous and photoactive Ti-MOF based on a novel tetranuclear [Ti2Tb2] cluster.

A robust and porous titanium metal-organic framework (Ti-MOF; LCU-505) has been solvothermally synthesized based on an unprecedented tetranuclear Ti2(µ3-O)2Tb2(µ2-CH3COO)2(H2O)4(OOC-)8 cluster (abbreviated as [Ti2Tb2]) and tritopic 4,4',4''-s-triazine-2,4,6-triyl-tribenzoic acid ligand (H3TATB). LCU-505 shows remarkable water stability and permanent porosity for N2 and CO2 gas adsorption. Moreover, LCU-505 demonstrates n-type semiconductor behavior and good photocatalytic activity in the degradation of organic dyes.

Mesoporous MOF Based on a Hexagonal Bipyramid Co8-Cluster: High Catalytic Efficiency on the Cycloaddition Reaction of CO2 with Bulky Epoxides.

A mesoporous cobalt-based metal-organic framework (LCU-606) was synthesized based on a hexagonal bipyramid Co8(µ4-O)3 cluster and an N,N,N',N'-tetrakis-(4-benzoic acid)-1,4-phenylenediamine ligand (H4TBAP). LCU-606 featuring large pore diameters of 21.7 Å and exposed Lewis-acid metal sites could serve as an excellent heterogeneous catalyst for CO2 cycloaddition reaction with various epoxide substrates under mild conditions (1 atm CO2, 60 °C, and solvent free). In particular, when extending the substrates to bulkier ones, LCU-606 still shows high catalytic efficiency on account of the large pore aperture. Also, LCU-606 demonstrates high recyclability and stability in consecutive catalytic runs. Therefore, the high efficiency, recyclability, and generality on CO2 catalytic cycloaddition make LCU-606 a very promising heterogeneous catalyst for CO2 chemical fixation.

Highly enhanced hydrazine oxidation on bifunctional Ni tailored by alloying for energy-efficient hydrogen production.

The low-potential hydrazine oxidation reaction (HzOR) can replace the oxygen evolution reaction (OER) and thus assemble with the hydrogen evolution reaction (HER), consequently achieving energy-saving hydrogen (H2) production. Notably, developing sophisticated bifunctional electrocatalysts for HER and HzOR is a prerequisite for efficient H2 production. Alloying noble metals with eligible non-precious ones can increase affordability, catalytic activity, and stability, alongside rendering bifunctionality. Herein, RuNi alloy deposited onto carbon (RuNi/C) was directly prepared by a simple and highly practical co-reduction method, showing excellent performance for HER and HzOR. Interestingly, to achieve 10 mA cm-2, RuNi/C only required an ultralow potential of 24 mV for HER, on par with commercial 20 wt% platinum in carbon (Pt/C), and -65 mV for HzOR, surpassing most reported counterparts. Moreover, the two-electrode electrolyzer only required small operation voltages of 57.8 and 327 mV to drive 10 and 100 mA cm-2, respectively. Driven by a homemade hydrazine (N2H4) fuel cell and solar panel, appreciable H2 yields of 1.027 and 1.406 mmol h-1 were achieved, respectively, exhibiting the energy-saving advantages alongside robust practicability. Moreover, theoretical calculations revealed that alloying with Ru endows bifunctional Ni sites not only with a lower H2O dissociation barrier but also with more favorable H* adsorption alongside the reduced energy barrier between HzOR intermediates.

Recent Progress in Research on [2.2]Paracyclophane-Based Dyes.

In recent years, the [2.2]paracyclophane (PCP) ring has attracted extensive attention due to its features of providing not only chirality and electron-donating ability but also steric hindrance, which reduces intermolecular π-π stacking interactions and thereby improves the fluorescence properties of dyes. To date, some circularly polarized luminescence (CPL)-active small organic molecules based on the PCP skeleton have been reviewed; however, the application of the PCP ring in improving the photophysical properties of fluorescent dyes is still limited, and new molecular design strategies are still required. This review summarizes and promotes the application of PCP in fluorescent dye design, fluorescence detection, and CPL modulation. We expect that this review will provide readers with a comprehensive understanding of the PCP skeleton and lead to further improvement in fluorescent dye design.

A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion.

A robust and porous titanium metal-organic framework (Ti-MOF; LCU-402) has been hydrothermally synthesized through combining a tetranuclear Ti2Ca2(µ3-O)2(µ2-H2O)1.3(H2O)4(O2C-)8 cluster and a tritopic 1,3,5-benzene(tris)benzoic (BTB) ligand. LCU-402 shows remarkable stability and permanent porosity for CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Moreover, LCU-402 as a heterogeneous catalyst can smoothly convert CO2 under a simulated flue atmosphere into organic carbonate molecules by cycloaddition reactions of CO2 and epoxides, indicating that LCU-402 might be a promising catalyst candidate in practical applications. We are confident that the identification of a persistent titanium-oxo building unit would accelerate the development of new porous Ti-MOF materials.

Robust acid-base Ln-MOFs: searching for efficient catalysts in cycloaddition of CO2 with epoxides and cascade deacetalization-Knoevenagel reactions.

A family of microporous and robust Ln(iii)-based metal-organic frameworks (1-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) have been obtained using 4,4',4''-nitrilotribenzoic acid (H3NTB) in NMP-HCl solvent. Both single-crystal and powder X-ray diffraction analyses demonstrate that 1-Ln are isostructural and possess 3D frameworks with permanent porosity for Ar and CO2 adsorption. Strikingly, the incorporation of both Lewis acidic lanthanide ions and the basic triphenylamine group into 1-Ln makes them efficient acid-base catalysts for both cycloaddition of epoxides with CO2 and one-pot cascade deacetalization-Knoevenagel reactions. The systematic catalytic studies show that 1-Tb and 1-Yb possess the best catalytic activities for both reactions, indicating the catalytic activities of these Ln-MOFs are strongly dependent on metal Lewis acid sites embedded in the frameworks.

Fluorescence Lifetime-Based Luminescent Thermometry Material with Lifetime Varying over a Factor of 50.

Recently, the growing demand for temperature detection is pushing forward the flourishing development of noncontact optical thermometry. Herein, a new red phosphor Sr2InTa1-xO6:xMn4+ (SIT:xMn4+) was first constructed and systematically investigated. Based on the fairly rapid decline of the lifetime from 0.403 to 0.008 ms by increasing the temperature from 25 to 450 K, a noncontact optical thermometer can be made from phosphor SIT:0.003Mn4+ with Sr = 1.396% K-1 at 375 K and Sa = 0.0012 K-1 at 300 K. Because the luminescence is based on the outermost 3d orbits of Mn4+, the lifetime of SIT:xMn4+ is quite sensitive to the temperature, leading to a rapid decline of the lifetime with the increase in temperature. Moreover, multiple rounds of variable-temperature studies were performed to demonstrate the stability and reversibility of SIT:0.003Mn4+. This work suggests that Mn4+-phosphors are promising candidates for application as optical thermometric material.

Ir nanoclusters/porous N-doped carbon as a bifunctional electrocatalyst for hydrogen evolution and hydrazine oxidation reactions.

One common iridium(III) complex was employed to facilely prepare ultrafine Ir nanoclusters embedded in porous N-doped carbon, which displayed significant bifunctional activity for both hydrogen evolution and hydrazine oxidation under alkaline conditions, enabling energy-efficient hydrogen production.

The synthesis of aryl-heteroaryl derivatives via the RhIII-catalyzed heteroarylation of arenes and heteroaromatic boronates.

An efficient RhIII-catalyzed strategy for constructing aryl-heteroaryl derivatives with removable ketoxime ether auxiliaries via direct C-H heteroarylation based on arenes and heteroaromatic boronates has been disclosed. This protocol could tolerate various pyridine, pyrimidine, pyrazole, thiophene, and furan heteroaromatic boronates well, providing the desired products with high reactivities and excellent regioselectivity. The easy synthetic accessibility may offer potential for application in the synthesis of heterocyclic drug molecules containing aryl-heteroaryl motifs.

Designing a Polyphosphate Polymorph of CsMg(PO3)3 as Host Lattice for Preparing Single Mn2+-Oxidation Doped Phosphor in the Open Environment.

Within Mn-activated phosphors, the oxidation state of Mn dopant strongly depends on the structural features of the host lattice. This paper reported a new polymorph of CsMg(PO3)3 (CMP) with a complicated three-dimensional (3D) framework of [Mg(PO3)3]∞ that is constructed by MgO6 octahedra and 1D infinite [PO3]∞ chains. Then we prepared a series of red phosphors CsMg1-x(PO3)3:xMn2+ (CMP:xMn2+) by high temperature solid state reactions in the open air. Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) studies revealed the single Mn2+-oxidation. Under 404 nm light exciting, CMP:0.2Mn2+ can emit single-band emission at around 630 nm with full-width at half-maximum (fwhm) of 70 nm. Besides, CMP:0.2Mn2+ possesses excellent thermostability up to 450 K. These features indicate that CMP:0.2Mn2+ is suitable to be used for LED backlight display. Moreover, this work suggests that a host lattice with suitable structure feature can form single Mn2+-oxidation and is rigid enough to protect Mn2+ from being oxidized by O2 at high temperature.

A series of microporous and robust Ln-MOFs showing luminescence properties and catalytic performances towards Knoevenagel reactions.

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show that 1-Ln are isostructural and have 3D porous frameworks with remarkable stability and permanent porosity for Ar and CO2 adsorption. In addition, 1-Ln exhibit diverse photoluminescence emissions depending on the nature of lanthanide ions. More importantly, 1-Ln are further studied in the Knoevenagel reactions of benzaldehyde derivatives and malononitrile under solvent-free conditions, and it is found that 1-Tb shows the best catalytic activities (yields up to 99%), providing a unique example to differentiate the roles of Ln ions within the frameworks in catalyzing Knoevenagel reactions.

Planar chiral [2.2]paracyclophanyl-based boron fluoride complexes: synthesis, crystal structure and photophysical properties.

Planar chiral [2.2]paracyclophanyl-based boron fluoride complexes (3a-3d) were designed and facilely synthesized. The X-ray structure study, theoretical calculations and CD spectra reveal the intense emission and planar chiral structures of these complexes. In particular, 3a-3d show moderate quantum yields and large Stokes shifts both in solution and solid state. Furthermore, the blue-shifted mechanochromic properties of 3a and 3b were both investigated in the solid state. This work is the first study on planar chiral boron monofluoride complexes within the boron fluoride complex field.

RhIII-Catalyzed Direct Heteroarylation of C(sp3)-H and C(sp2)-H Bonds in Heterocycles with N-Heteroaromatic Boronates.

Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)-H and C(sp2)-H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents. The direct heteroarylation method could supply potential application in terms of the synthesis of drug molecules with multiple heterocycles.

Natural DNA-assisted RuP2 on highly graphitic N,P-codoped carbon for pH-wide hydrogen evolution.

Natural DNA was employed for the first time as a phosphorization agent and carbon source to controllably synthesize a RuP2/N,P-codoped carbon composite by a simple "mix-and-pyrolyze" strategy, which displays higher activity for alkaline and acidic HER and neutral activity compared to Pt/C together with outstanding durability.

RhIII-Catalyzed C-H (Het)arylation/Vinylation of N-2,6-Difluoroaryl Acrylamides.

RhIII-catalyzed sp2 C-H cross-coupling of acrylamides with organoboron reactants has been accomplished using a commercially available N-2,6-difluoroaryl acrylamide auxiliary. A broad range of aryl and vinyl boronates as well as a variety of heterocyclic boronates with strong coordinating ability can serve as the coupling partners. This transformation proceeds under moderate reaction conditions with excellent functional group tolerance and high regioselectivity.