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An aliovalent mixed-metal framework DUT-174 [LiAl(2-methylimidazolate)4]n, isostructural to ZIF-8, was synthesized from lithium aluminum hydride (LiAlH4) and 2-methylimidazole (2-mImH) through dehydrogenation. Lithium and aluminum cations acting as alternating framework nodes are coordinated tetrahedrally by (2-mIm)-. DUT-174 has a high specific surface area of 1149 m2 g-1 and CO2 uptake of 11.57 mmol g-1 at 195 K.This work presents the restoration of the Zr-phthalate coordination polymer (Zr-Ph CP) via valuable application in photocatalysis. Zr-Ph CP was facilely synthesized using a soft hydrothermal method at 70 °C, and was characterized utilizing FTIR, Raman Spectrosopy, XPS, PXRD, SEM/EDX, BET, and a hyperspectral camera. Assessment of its photocatalytic degradation potential was performed against two different dyes, the cationic methylene blue (MB) and the anionic methyl orange (MO), as frequent models of organic contaminants, under properly selected mild visible illumination (9 W) where the bandgap energy (Eg) was determined to be 2.72 eV. Effects of different initial pH values and different dyes' initial concentrations were covered. Photocatalytic degradation studies showed that Zr-Ph CP effectively degraded both dyes for initial pH 7 within about 40-60 minutes. Degradation rate constants were calculated as 0.17 and 0.13 min-1 for MB and MO, respectively. Generally, both direct and indirect mechanisms share in the degradation, where adsorption has shown an important role. The repeated use of Zr-Ph CP does not significantly affect its photocatalytic performance suggesting high water stability.Visible-light-promoted [2 + 2] cycloaddition provides a straightforward and efficient way to produce cyclobutanes, which are the core skeleton in commercial pharmaceuticals and fine chemicals. However, the control of the conformation to produce syn-head-to-head (syn-HH) cyclobutanes remains a grand challenge. In this work, we report the design and synthesis of anthraquinone-based metal-organic cages (MOCs) for the [2 + 2] photocycloaddition of chalcones to generate syn-HH cyclobutanes. Guided by the coordination-driven self-assembly strategy, one D2 and three D4h symmetric MOCs are constructed from anthraquinone-derived dicarboxylate linkers and 4-tert-butylsulfonylcalixarene capped tetrametallic clusters. The porous cages feature large hydrophobic cavities and photoactive anthraquinone units and are demonstrated to be efficient and recyclable photocatalysts for [2 + 2] cycloaddition of chalcones. The syn-HH diastereomers are obtained with up to 13 1 diastereomeric ratio (dr). The cage catalysts provide a well-defined confined space to accommodate the substrates, thus leading to enhanced selectivity relative to the free anthraquinone catalyst.Two coordination polymers, [M(5-hip)(H2O)3]n (M = Cd2+ (1), Zn2+ (2), 5-hip = 5-hydroxyisophthalic acid), have been synthesized under hydrothermal conditions. The crystal structure reveals that complexes 1 and 2 have 1D chain structures by the coordination of metal ions and 5-hip. 1D chains are connected by hydrogen bonds to form a 3D structure. AC impedance analysis shows that the proton conductivity of complexes 1 and 2 comes up to 1.58 × 10-3 S cm-1 (98%RH, 343 K) and 5.27 × 10-4 S cm-1 (98%RH, 353 K), respectively. To further improve the proton conductivity, a hybrid membrane was prepared by the solution casting method with complexes as fillers and sulfonated polyether ether ketone (SPEEK) as the organic matrix. The proton conductivity of hybrid membranes 1@SPEEK-5 and 2@SPEEK-5 is 1.97 and 1.58 times higher than that of pure SPEEK membranes, respectively. Furthermore, the two complexes are excellent fluorescent sensors, which could detect Cr2O72- in aqueous solution with high sensitivity and selectivity. Both of them have low detection limits for Cr2O72- in aqueous solution, where the detection limit of complex 1 is 0.8 μM and that of complex 2 is 1 μM. The above work demonstrates that the two complexes are dual-functional materials with high proton conduction and good fluorescence properties.The principles of the design of responsive luminescent probes and sensors based on lanthanide emission are summarised, based on a mechanistic understanding of their mode of action. Competing kinetic pathways for deactivation of the excited states that occur are described, highlighting the need to consider each of the salient quenching processes. Such an analysis dictates the choice of both the ligand and its integral sensitising moiety for the particular application. The key aspects of quenching involving electron transfer and vibrational and electronic energy transfer are highlighted and exemplified. Responsive systems for pH, pM, pX and pO2 and selected biochemical analytes are distinguished, according to the nature of the optical signal observed. Selleck PF-06826647 Signal changes include both simple and ratiometric intensity measurements, emission lifetime variations and the unique features associated with the observation of circularly polarised luminescence (CPL) for chiral systems. A classification of responsive lanthanide probes is introduced. Examples of the operation of probes for reactive oxygen species, citrate, bicarbonate, α1-AGP and pH are used to illustrate reversible and irreversible transformations of the ligand constitution, as well as the reversible changes to the metal primary and secondary coordination sphere that sensitively perturb the ligand field. Finally, systems that function by modulation of dynamic quenching of the ligand or metal excited states are described, including real time observation of endosomal acidification in living cells, rapid urate analysis in serum, accurate temperature assessment in confined compartments and high throughput screening of drug binding to G-protein coupled receptors.Due to their ultra-thin morphology, larger specific surface area and more exposed active sites, two-dimensional (2D) metal-organic framework (MOF) nanosheets can break the limitations of three-dimensional (3D) MOFs in sensitivity, response speed and the limit of detection for sensing applications. In this work, fluorescent NH2-MIL-53(Al) nanosheets were developed as a fluoride detection sensor compared with the 3D bulk counterpart. The morphological and structural characteristics of the obtained products were systematically characterized, and the favourable chemical and fluorescence stability of the NH2-MIL-53(Al) nanosheets were explored. The fluorescent NH2-MIL-53(Al) nanosheets showed high sensitivity, fast response speed (as short as 10 seconds), low limit of detection (15.2 ppb), and wide linear detection range (5-250 μM), and all performances were better than those of their bulk counterpart. In addition, the sensing mechanism was investigated to be based on the transformation of the NH2-MIL-53(Al) framework that induced the release of fluorescent ligands, resulting in an exceptionally enhanced fluorescence. This work highlights the advantages of 2D MOF nanosheets in fluorescence sensing applications.Several organic salts based on the combination of two different choline derivative cations and MnCl3-, GdCl4- and TbCl4- as anions were immobilized in mesoporous silica nanoparticles (MSNs) by a two-step synthetic method. Firstly, MSNs were functionalized with choline derivative cations with chloride anions and then the metals were incorporated by the reaction of the chloride with the respective metal chloride salts. These nanomaterials were fully characterized by different characterization techniques such as 1H-NMR, FT-IR, elemental analysis, TEM, TGA, N2 adsorption, XRD and DLS. These characterization data were important to confirm the successful functionalization of the nanomaterials and to access their textural properties and colloidal stability. The final materials were also characterized by ICP-MS that indicated the metal contents. The cytotoxicity profile was evaluated in four different cell lines (3T3, 293T, HepG2 and Caco-2), which shows some relevant differences between the metal organic salts and their immobilized analogues.This review describes the recent advances made in difluoromethylation processes based on X-CF2H bond formation where X is C(sp), C(sp2), C(sp3), O, N or S, a field of research that has benefited from the invention of multiple difluoromethylation reagents. The last decade has witnessed an upsurge of metal-based methods that can transfer CF2H to C(sp2) sites both in stoichiometric and catalytic mode. Difluoromethylation of C(sp2)-H bond has also been accomplished through Minisci-type radical chemistry, a strategy best applied to heteroaromatics. Examples of electrophilic, nucleophilic, radical and cross-coupling methods have appeared to construct C(sp3)-CF2H bonds, but cases of stereoselective difluoromethylation are still limited. In this sub-field, an exciting departure is the precise site-selective installation of CF2H onto large biomolecules such as proteins. The formation of X-CF2H bond where X is oxygen, nitrogen or sulfur is conventionally achieved upon reaction with ClCF2H; more recently, numerous protocols have achieved X-H insertion with novel non-ozone depleting difluorocarbene reagents. All together, these advances have streamlined access to molecules of pharmaceutical relevance, and generated interest for process chemistry.Cu-Zn disorder is known to deeply affect kesterite (Cu2ZnSnS4, CZTS) due to the low temperature order-disorder phase transition, leading to a random occupation of the two cations in the shared crystallographic planes. This defect complex has been extensively studied in the thin film photovoltaic sector, with considerable efforts in developing methods to quantify disorder. In this study, a preliminary investigation of thermoelectric properties in temperature for thin film CZTS is presented. It is found that Cu-Zn disorder enhances both electrical conductivity and Seebeck coefficient. This can positively affect the thermoelectric performance, showing a mechanism of potential interest for a broad class of quaternary chalcogenides. The order-disorder transition is clearly visible in the electronic properties. This feature is repeatable, with samples from different preparations and groups showing consistent results, qualitatively suggesting electronic measurements as possible methods to quantify disorder. Furthermore, the reversibility of the transition allows the electronic properties to be tuned via specific thermal treatments, pointing to interesting applications in tunable electronics.Chiral metasurfaces patterned with L-shaped holes in a thin film of Dirac semimetal Cd3As2 are designed. The impact of temperature T on circular conversion dichroism, mainly characterized by circular polarization differential transmittance (CPDT), is studied by rigorous coupled-wave analysis. The results show that decreasing T will give rise to the appearance of much more narrow CPDT peaks and dips, and the maximum differential transmittance between two opposite circularly polarized light can reach above 0.60 by optimizing the structural parameters at 80 K. As the T increases, the differential transmittance gradually decreases, and the CPDT peak and dip values exhibit variation tendencies of 'Z' and 'S' types, respectively. Two simple formulae of CPDT extreme values with respect to T are derived, predicting that the decreasing tendency will reach saturation when T ≥ 500 K. Differing from the wavelength-independent variation trend of differential transmittance, CPDT extremum positions mainly show a blueshift (redshift) tendency at the wavelength λ > 10 μm (λ less then 5 μm) as the T increases.
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