Preparation and solar-light photocatalytic activity of TiO2 composites: TiO2/kaolin,TiO2/diatomite,and TiO2/zeolite

Three TiO₂ loaded composites, TiO₂/kaolin, TiO₂/diatomite, and TiO₂/zeolite, were prepared in order to improve the solar-light photocatalytic activity of TiO₂. The results showed that the photocatalytic activity could obviously be enhanced by loading appropriate amount of inorganic mineral materials. Meanwhile, TiO₂ content, heat-treatment temperature and heat-treatment time on the photocatalytic activity were reviewed. Otherwise, the effect of solar light irradiation time and dye concentration on the photocatalytic degradation of Acid Red B was investigated. Furthermore, the degradation mechanism and adsorption process were also discussed.     

Rationally Investigating the Influence of T1 Location on Electroluminescence Performance of Aryl Amine Modified Phosphine Oxide Materials

The correspondence between triplet location effect and host‐localized triplet–triplet annihilation and triplet–polaron quenching effects was performed on the basis of a series of naphthyldiphenylamine (DPNA)‐modified phosphine oxide hosts. The number and ratio of DPNA and diphenylphosphine oxide was adjusted to afford symmetrical and unsymmetrical molecular structures and different electronic environments. As designed, the first triplet (T₁) states were successfully localized on the specific DPNA chromophores. Owing to the meso‐ and multi‐insulating linkages, identical optical properties and comparable electrical performance was observed, including the same first singlet (S₁) and T₁ energy levels to support the similar singlet and triplet energy transfer and the close frontier molecular orbital energy levels. This established the basis of rational investigation on T₁ location effect without interference from other optoelectronic factors.     

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

We present the isolation of the first mononuclear dihalogermylene, and mono‐ and dinuclear stannylene complexes of transition metals. These exhibit exceptionally pyramidalized Group 14 centers. Additionally, removal of the halide substituents from the Ge/Sn atom was successfully performed in two ways, halide abstraction and reduction, leading to a variety of unusual structural motifs.     

Highly Enantioselective Ring‐Opening Reactions of Aziridines with Indole and Its Application in the Building of C3‐Halogenated Pyrroloindolines

A magnesium‐catalyzed asymmetric ring‐opening reaction of aziridine with indole has been realized by employing commercially available chiral ligands. Both of the enantiomers of the ring‐opening product could be obtained with good yields and a high level of enantioselectivity. The corresponding ring‐opening product could be further transformed to various types of enantioenriched C₃‐halogenated‐pyrroloindolines.     

Semiconductor and Metallic Core–Shell Nanostructures: Synthesis and Applications in Solar Cells and Catalysis

Nano‐heterostructures have attracted great attention due to their extraordinary properties beyond those of their single‐component counterparts. This review focuses on a specific type of hybrid structures: core–shell structures. In particular, we present and discuss the recent wet‐chemical synthesis approaches for semiconductor and metallic core–shell nanostructures, and their relevant properties and potential applications in photovoltaics and catalysis, respectively.     

Facile Access to cis‐2,6‐Disubstituted Tetrahydropyrans by Palladium‐Catalyzed Decarboxylative Allylation: Total Syntheses of (±)‐Centrolobine and (+)‐Decytospolides A and B

cis‐2,6‐Tetrahydropyran is an important structural skeleton of bioactive natural products. A facile synthesis of cis‐2,6‐disubstituted‐3,6‐dihydropyrans as cis‐2,6‐tetrahydropyran precursors has been achieved in high regio‐ and stereoselectivity with high yields. This reaction involves a palladium‐catalyzed decarboxylative allylation of various 3,4‐dihydro‐2H‐pyran substrates. Extending this reaction to 1,2‐unsaturated carbohydrates allowed the achievement of challenging β‐C‐glycosylation. Based on this methodology, the total syntheses of (±)‐centrolobine and (+)‐decytospolides A and B were achieved in concise steps and overall high yields.     

Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles

A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF₃‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed.     

Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation

The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O^?.) is an important species in C?H activation. The mechanistic details of C?H activation by O^?. radicals can be well understood by studying the reactions between O^?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc₂O₃)_NO^? (N=1–18) clusters was observed. The reactivity of (Sc₂O₃)_NO^? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc₈O₁₃^?) and 12 (Sc₂₄O₃₇^?). Larger (Sc₂O₃)_NO^? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc₂O₃)_NO^? (N=1–5) clusters, which were found to contain the O^?. radicals as the active sites. The local charge environment around the O^?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O^?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation.     

Calcite Microneedle Arrays Produced by Inorganic Ion‐Assisted Anisotropic Dissolution of Bulk Calcite Crystal

Besides studies on the mineralization process, research on the demineralization of minerals provides another way to understand the crystallization mechanism of biominerals and fabricate crystals with complicated morphologies. The formation of ordered arrays of c‐axis‐oriented calcite microneedles with a tri‐symmetric structure and lengths of more than 20 μm was realized on a large scale for the first time through anisotropic dissolution of calcite substrates in undersaturated aqueous solution in the presence of ammonium salts. The lengths and the aspect ratios of the calcite microneedles can be tuned by simply changing the concentrations of the ammonium salts and the dissolution time. The shape of the transverse cross sections of the calcite microneedles obtained in the presence of NH₄Cl and NH₄Ac is almost regularly triangular. The tri‐symmetric transverse cross‐section geometry of the calcite microneedles could be attributed to the tri‐symmetric feature of rhombohedral calcite atomic structures, the synergetic interactions between electrostatic interaction of ammonium ions and dangling surface carbonate groups, and the ion incorporation of halide ions.     

Oligosiloxane Functionalized with Pendant (1,3‐Bis(9‐carbazolyl)benzene) (mCP) for Solution‐Processed Organic Electronics

A new oligosiloxane derivative (ODCzMSi) functionalized with the well‐known 1,3‐bis(9‐carbazolyl)benzene (mCP) pendant moiety, directly linked to the silicon atom of the oligosiloxane backbone, has been synthesized and characterized. Compared to mCP, the attachment of the oligosiloxane chain significantly improves the thermal and morphological stabilities with a high decomposition temperature (T_d=540 °C) and glass transition temperature (T_g=142 °C). The silicon–oxygen linkage of ODCzMSi disrupts the backbone conjugation and maintains a high triplet energy level (E_T=3.0 eV). A phosphorescent organic light‐emitting diode (PhOLED) using iridium bis(4,6‐difluorophenyl)pyridinato‐N,C² picolinate (FIrpic) as the emitter and ODCzMSi as the host shows a relatively low turn‐on voltage of 5.0 V for solution‐processed PhOLEDs, maximum external quantum efficiency of 9.2 %, and maximum current efficiency of 17.7 cd A^?1. The overall performance of this device is competitive with the best reported solution‐processed blue PhOLEDs. Memory devices using ODCzMSi as an active layer exhibit non‐volatile write‐once read‐many‐times (WORM) characteristics with high stability in retention time up to 10⁴ s and a low switch on voltage. This switching behaviour is explained by different stable conformations of ODCzMSi with high or low conductivity states which are obtained under the action of electric field through a π–π stacking alignment of the pendant aromatic groups. These results with both PhOLEDs and memory devices demonstrate that this oligosiloxane–mCP hybrid structure is promising and versatile for high performance solution‐processed optoelectronic applications.