Latest ArticlesPhotosynthesis is the process through which living plants utilize photosynthetic pigments, such as chlorophyll, to convert CO2 and water into organic compounds and release O2 under visible light. In this study, we have successfully constructed a fluorescent supramolecular polymer (P5Py2/Zn/Gen)n by employing orthogonal pillar[5]arene-based molecular recognition and metal ion coordination. Within the supramolecular polymer, the guest molecule Gen unit acts as a light-harvesting moiety, as the ACQ effect is inhibited by host-guest interactions, while the (Py)2/Zn center serves as a catalytic site. By employing this orthogonal self-assembly strategy, we have enhanced the stability of both the donor and acceptor in catalyzing the reduction of p-nitrophenol to p-aminophenol. Moreover, this photocatalyst can be reused at least 5 times without significant conversion loss. These findings provide a pathway for constructing a recyclable artificial LHS that mimics the entire photosynthesis process.
In recent years, FeCl3-photocatalyzed direct C–H/Si–H bond functionalization reactions have attracted huge attention. In those transformations, chlorine radical (Cl•) could be generated from FeCl3 via a ligand-to-metal charge transfer (LMCT)/homolysis process under light irradiation. The resulting chlorine radical subsequently acts as a hydrogen atom transfer (HAT) agent to abstract the hydrogen atom of aliphatic C–H, O–H, or Si–H bonds to give the corresponding C/Si/O-centered radicals for various organic transformations. In this review, we summarized the recent advances in the application of FeCl3 as a HAT photocatalyst for the C/Si–H functionalization to construct C–C, C–N, C–Si, C–S, C–B, and C-P bonds.
The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na+/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region, leading to inferior cycling performance. Additionally, they exhibit unsatisfactory stability when exposed to water for extended periods. To address these challenges, we propose a Cu/Ti co-doped P3-type cathode material (Na0.67Ni0.3Cu0.03Mn0.6Ti0.07O2), which effectively mitigates Na+/vacancy ordering and suppresses P3-O3 phase transitions at high voltages. As a result, the as-prepared sample exhibited outstanding cyclic performance, with 81.9% retention after 500 cycles within 2.5–4.15 V, and 75.7% retention after 300 cycles within 2.5–4.25 V. Meanwhile, it demonstrates enhanced Na+ transport kinetics during desodiation/sodiation and reduced growth of charge transfer impedance (Rct) after various cycles. Furthermore, the sample showed superb stability against water, exhibiting no discernible degradation in structure, morphology, or electrochemical performance. This co-doping strategy provides new insights for innovative and prospective cathode materials.
A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal- and photosensitizer-free conditions. This newly developed strategy provides straightforward and efficient access to diverse value-added vicinal trifluoromethyl amines without resorting to the pre-functionalized reagents. Mechanistic experiments demonstrate that the approach proceeded through CF3 and iminyl two-radicals process, which were generated directly from commercially available benzophenone imine in a novel electron-donor mode via a SET process activated by the bifunctional hypervalent iodine reagents. The synthetic potential of the protocols was further showcased via the condensation/amination sequential cascade, and transformations to access β-CF3 primary amines.
Dynamic covalent imine reactions between 2′,3′-dimethoxy-[1,1′:4′, 1″-terphenyl]-3,3″,5,5″-tetracarbaldehyde (DMTT) and cyclohexanediamine, p-phenylenediamine, and benzidine, respectively, generate a porous organic cage (DMPOC) and two covalent organic frameworks (COFs), USTB-29, and USTB-30. DMPOC shows a [3 + 6] topological cage-like structure according to single crystal X-ray diffraction result. In contrast, both microcrystalline USTB-29 and USTB-30 exhibit two-dimensional monoporous structures in an eclipsed AA stacking style based on powder X-ray diffraction and theoretical simulations. In addition, DMPOC is capable of efficiently absorbing the iodine vapor with an outstanding uptake of 5.10 g/g, much higher than that of USTB-29 (3.07 g/g) and USTB-30 (3.16 g/g). Cage to COFs transformations have been realized from DMPOC to USTB-29 and USTB-30 via the imine bond exchange with slightly increased iodine vapor uptake. Mechanism investigations uncover that both nitrogen and oxygen atoms of POC and COFs contribute to iodine vapor capture due to the formation of charge transfer matter, and loose interaction introducing adaptive expanding voids of DMPOC is suggested to capture more iodine vapor than that of COFs with strong π-π interactions.
The composite polymer electrolyte has been obtained via incorporating LiCUST-701 (a new metal–organic rotaxane framework modified by Li+) into poly(ethylene oxide) (PEO) matrix and give a high ionic conductivity of 4.02 × 10−4 S/cm at 60 ℃. DFT calculations were used to visualize the possible diffusion pathway of Li+. The all-solid-state cell assembled with LiFePO4, composite polymer electrolyte and lithium metal foil delivered with excellent cycling capability and stability even under high current densities.
Direct X-ray detectors, which directly convert X-rays into electrical signals through semiconductors, have higher space solution than scintillator-mediated indirect X-ray ones and are high desirable for early cancer detection and other applications, but the mainstream commercial α-Se detector is still largely limited by high production costs, large leakage current and low stability. This article reports an easily prepared, stable radiochromic semiconductive metal–organic framework (MOF), (MV)[Cd3(tdc)4]·2H2O (RCS-1, H2tdc = 2,5-thiophenedicarboxylic acid; MV2+ = methyl viologen cation) with direct X-ray detecting ability. With a large bulk resistivity of 8.40 × 109 Ω cm, this material ensures minimal dark current and low noise for X-ray detection. Additionally, it exhibits higher sensitivity to W Kα X-rays (98.58 µC Gy−1 cm−2) than α-Se (~20 µC Gy−1 cm−2). Meanwhile, unlike most reported direct X-ray detecting semiconductors, compound RCS-1 shows remarkable color change upon X-ray irradiation owing to the presence of photochromism-active viologen cations. This feature offers an appealing visual detecting ability to direct X-ray detectors that provide only the electrical signals.
The research of long persistent luminescence (LPL) materials has yield brilliant results in many fields. However, the efforts are still needed for the regulation of the LPL performance. In this work, a series of LPL metal organic halides with rich halogen-bond interactions, Py-CdX2 (X = Cl, Br, I) were synthesized through self-assembly by CdX2 and pyridine solvent. The steady-state emission redshifted and phosphorescence lifetime declined as the halogen atoms are aggravated. Three halides exhibit adjustable emission from blue to green and multiple phosphorescence from green to yellow at room temperature by changing the excitation wavelengths. Surprisingly, Py-CdX2 can emit the visible color-tunable LPL from green to yellow after removing different excitation sources at ambient conditions. Combing the results of theoretical calculation and experimental analysis, it is found that heavy atom effect and the rich intermolecular halogen bond help realize LPL and multiple triplet states originated from the pyridine ring and the halogens.
Finding suitable strategies to effectively enhance the optical properties of materials are the goal being pursued by researchers. Herein, cation-anion synergetic interactions strategy was proposed to develop two novel organic-inorganic hybrid antimony-based optical materials, (C3H5N2)SbF2SO4 (Ⅰ) and (C5H6N)SbF2SO4 (Ⅱ), which were obtained by introducing Sb3+cation containing stereochemically active lone-pair (SCALP) and organic π-conjugated cations into sulphate system. The synergistic interactions of the organic π-conjugated cations, the inorganic [SbO2F2]3− seesaw anions and the [SO4]2− distorted tetrahedra anions make their ultraviolet (UV) absorption edges approach 297 and 283 nm, respectively, and raise their birefringence up to 0.193@546 nm and 0.179@546 nm, respectively. Interestingly, although the two compounds have the same stoichiometric ratio and similar one-dimensional (1D) chain structure, they show opposite macroscopic symmetry, where the NCS compound (Ⅱ) exhibits a large second-harmonic generation (SHG) response (1.6 times that of KH2PO4). The two reported compounds are found to be promising UV optical materials in the experimental tests.
Hypercrosslinked polymers (HCPs) with large surface areas, high intrinsic porosities and low production costs may be available platforms for iodine capture. However, the lack of iodine-philicity binding sites limits their adsorption capacity. Here we use vapor-phase postsynthetic amination strategy to introduce electron-donating amino groups into the prefabricated HCPs for enhancing their iodine capture performance. Through simple vapor-phase exposure, the halogen-containing HCPs can be grafted by amines through nucleophilic substitution toward chloro groups. Combining with the abundant amino groups and high porosities, the amino-functionalized porous polymers show substantially increased iodine adsorption capacity, about 221% as that of original one, accompanied by excellent recyclability. Mechanism investigations reveal the key roles of the electron-donor amino groups and π-conjugated benzene rings along with structure characteristics of porous polymer frameworks in iodine capture. Moreover, this vapor-phase amination strategy shows good generality and can be extended to various amines, e.g., ethylenediamine, 1,3-diaminopropane and diethylenetriamine. Our work proves that this simple vapor-phase postsynthetic functionalization strategy may be applied in other porous polymers with wide application prospects in adsorption, separation and storage.
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