A new method for synthesizing terminal olefins from esters using the Corey-Chaykovsky reagent.

A new method for the synthesis of terminal olefins was developed through the reaction of the Corey-Chaykovsky reagent (dimethyl-sulfonium methylide) with readily available esters. After the domino process of nucleophilic addition, elimination and rearrangement in one pot, the terminal olefins were synthesized in high yields (up to 84%) under mild conditions. The synthetic method was well tolerated by many functional groups and a new route for the synthesis of various terminal olefin derivatives is provided. In the end, a possible reaction mechanism is proposed, which is supported by DFT calculations.

Preparation of Hybrid Nanopigments with Excellent Environmental Stability, Antibacterial and Antioxidant Properties Based on Monascus Red and Sepiolite by One-Step Grinding Process.

This study is focused on the preparation, characterization, and multifunctional properties of intelligent hybrid nanopigments. The hybrid nanopigments with excellent environmental stability and antibacterial and antioxidant properties were fabricated based on natural Monascus red, surfactant, and sepiolite via a facile one-step grinding process. The density functional theory calculations demonstrated that the surfactants loaded on sepiolite were in favor of enhancing the electrostatic, coordination, and hydrogen bonding interactions between Monascus red and sepiolite. Thus, the obtained hybrid nanopigments exhibited excellent antibacterial and antioxidant properties, with an inhibition effect on Gram-positive bacteria that was superior to that of Gram-negative bacteria. In addition, the scavenging activity on DPPH and hydroxyl free radicals as well as the reducing power of hybrid nanopigments were higher than those of hybrid nanopigments prepared without the addition of the surfactant. Inspired by nature, gas-sensitive reversible alochroic superamphiphobic coatings with excellent thermal and chemical stability were successfully designed by combining hybrid nanopigments and fluorinated polysiloxane. Therefore, intelligent multifunctional hybrid nanopigments have great application foreground in related fields.

Spectral investigation on single molecular optoelectronics of ladder phenylenes.

Atomic chains and organic conjugated molecules are of great important research value in molecular optoelectronics, due to their special optoelectronic properties. The fully conjugated nature of ladder phenylenes (LPs) provide some unique properties that have potential applications in the fabrication of molecular electronics devices. Our results reveal optoelectronic properties apply density function theory and non-equilibrium green's function theory, including unit-dependent light absorption, Raman scattering, phonon energy band structure, the chemical potential dependent density of states, electrical conductivity, I-V curve, transmission spectrum, etc. Our research provides theoretical guidance for the regulation of light-harvesting regions based on LPs structures, and theoretical support for the design of nano-scale optoelectronic devices.

Organic photoredox catalytic amino-heteroarylation of unactivated olefins to access distal amino ketones.

Here we describe a metal-free amino-heteroarylation of unactivated olefins via organic photoredox catalysis, providing a concise and efficient approach for the rapid synthesis of various δ (ß, ε)-amino ketones under mild conditions. This protocol demonstrates that the new photocatalyst Cz-NI developed by our group has an excellent photoredox catalytic performance. Finally, a series of mechanistic experiments and DFT calculations indicate that this transformation undergoes a photoredox catalytic sequential radical addition/functional group migration process.

Incorporation of Different Metal Ion for Tuning Color and Enhancing Antioxidant Activity of Curcumin/Palygorskite Hybrid Materials.

Curcumin is one of the dietary dyes extracted from turmeric and used for prevention and treatment of various illnesses. However, the low bioavailability and poor stability of curcumin limits its relevant applications. Therefore, different metal ions including Cu2+, Zn2+, Mg2+, Al3+, or Fe3+ were incorporated to tune the color, enhance the environmental stability and antioxidant activity of curcumin in the presence of palygorskite in this study. The as-prepared samples were studied using X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Zeta potential, and transmission electron microscopy. In addition, the density functional theory calculation was also performed to explore the possible interaction among metal ions, curcumin and palygorskite. It was found that the color changing and stability enhancing were ascribed to the curcumin-metal ions coordination as well as chemical interactions between curcumin-metal complex and palygorskite. Moreover, the as-prepared composites showed more excellent color, thermal stability, antioxidant activity, and fluorescence properties than that of the curcumin/palygorskite composites due to the presence of metal ions. The finding of this investigation may contribute to developing the multifunctional composites with different colors and good antioxidant activity for relevant applications based on curcumin and palygorskite.

Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated aza-heterocycles.

A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Brønsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.

Dehydrogenation/(3+2) Cycloaddition of Saturated Aza-Heterocycles via Merging Organic Photoredox and Lewis Acid Catalysis.

Herein, we report a photoinduced dehydrogenation/(3+2) cycloaddition reaction by merging organic photoredox and Lewis acid catalysis, providing a straightforward and efficient approach for directly installing a benzofuran skeleton on the saturated aza-heterocycles. In this protocol, we also describe a novel organic photocatalyst (t-Bu-DCQ) with the advantages of a wider redox potential, easy synthesis, and a low price. Furthermore, the stepwise activation mechanism of dual C(sp3)-H bonds was demonstrated by a series of experimental and computational studies.

Tandem Michael Addition-Cyclization of Nitroalkenes with 1,3-Dicarbonyl Compounds Accompanied by Removal of Nitro Group.

A tandem Michael addition-cyclization of nitroalkenes with 1,3-dicarbonyl compounds was developed using phase transfer catalyst (PTC), allowing for the synthesis of polysubstituted-[4,5]-dihydrofuran in high yields. A wide range of substrates were demonstrated by this one-step process. Meanwhile, nitro group was substituted to form corresponding nitrite ion detected in the aqueous phase providing a reasonable pathway for denitrating poisonous and explosive nitro-containing compounds. The proposed mechanism was also supported by our DFT calculations.

Physical mechanisms of photoinduced charge transfer in neutral and charged donor-acceptor systems.

In this paper, we provide visualization methods to reveal the physical mechanisms of photoinduced charge transfer in neutral and charged donor-acceptor systems. These visualization methods use the charge density difference and transition density matrix, which can promote deeper understanding of photoinduced charge transfer in donor-acceptor systems.

Optical properties of S2 and S3 excited states of protonated schiff-base retinal chromophores in TPA, ECD and ROA.

The electronic transitions of the protonated Schiff base of 1l-cis-retinal (PSB11) and protonated Schiff bases of all-trans retinal (PSBT) for the second or higher electronic excited states are hard to be observed experimentally, due to weak intensities of electronic state excitations. In this paper, we propose visualizations method to investigate these weak electronic state transitions of PSB11 and PSBT, using two-photon absorption (TPA), electronic circular dichroism (ECD) and Raman optical activity (ROA) spectra. Because of the resonance excitations of PSB11 and PSB11 in TPA, the transition intensity of the third electronic state is significantly enhanced, which are much larger than that of S1 and S2 electronic transitions. The charge transfer and electron-hole coherence of these electronic transitions in each step in TPA are visualized with charge difference density and transition density matrix. Also, the strong absorptions of S1 and S2 electronic excited states are observed with ECD spectra, and the physical mechanism of electric and magnetic interactions for these electronic transitions are revealed by visualization method. The large intensity of ROA at S3 excited state results from transition electric and magnetic dipole interactions, not from transition electric dipole and transition electric quadrupole interactions. Our results provide a new visualization method to study the optical properties of biological system using TPA and ECD spectra.

Photoinduced charge transfer in quasi-one-dimensional polymers in two-photon absorption.

In this work, we theoretically investigate the structure and the transition characteristics of one- (OPA) and two-photon absorption (TPA) spectra of different length neutral and charged thiophene polymers. The effects and regulation of different charges on photoinduced charge transfer are discovered and their physical mechanisms are explained. We find that both the OPA and TPA spectra undergo a sizeable redshift after the charge is injected into the polymer, and the redshift after the positive charge injection is excellent. The alternating charge transfer that occurs in a two-photon transition of a charged system is derived from the alternating distribution of charge (dipole moment) in the dynamics of the system. To study the gradual behavior of infinite polymers, we also theoretically calculated the optical properties and electronic structures of infinitely long thiophene polymers under different electrical charge injections by a one-dimensional periodic model. The redshift of the OPA and TPA spectra is found to be due to orbital energy level movement.

Density functional theory studies of thermal activation of methane by MH+ (M = Ru, Rh, and Pd).

The dehydrogenation reaction mechanisms of methane catalyzed by a ligated transition metal MH(+) (M = Ru, Rh, and Pd) have been investigated theoretically. Activation of methane by MH(+) complexes is proposed to proceed in a one-step manner via one transition state: MH(+) + CH(4) --> MH(+)CH(4) --> [TS] --> (MCH(3)(+))H(2) -->MCH(3)(+) + H(2). Both high-spin and low-spin potential energy surfaces are characterized in detail. Our calculations indicate that the ground-states species have low electron spin and a dominant 4d(n) configuration for RuH(+), RhH(+), and PdH(+), and the whole reaction proceeds on the ground-states potential energy surfaces with a spin-allowed manner. The MH(+) (M = Ru, Rh, and Pd) complexes are expected from the general energy profiles of the reaction pathways to efficiently convert methane to metal methyl, thus RuH(+), RhH(+), and PdH(+) are likely to be excellent mediators for the activity of methane. In the reactions of MH(+) with methane, the H(2) elimination from the dihydrogen complex is quite facile without barriers. The exothermicities of the reactions are close for Ru, Rh, and Pd: 11.1, 1.2, and 5.2 kcal/mol, respectively.

Density functional theory study of the platinum-catalyzed cyclopropanation reaction with olefin.

A computational study of the platinum-catalyzed cyclopropanation reaction with olefin is presented. The model system is formed by an ethylene molecule and the active catalytic species, which forms from a CH2 fragment and the Cl2Pt(PH3)2 complex. The results show that the active catalytic species is not a metal-carbene of the type (PH3)2Cl2Pt=CH2 but two carbenoid complexes which can exist in almost two degenerate forms, namely (PH3)2Pt(CH2Cl)Cl (carbenoid A) and (PH3)Pt(CH2PH3)Cl2 (carbenoid B). The reaction proceeds through three pathways: methylene transfer, carbometalation for carbenoid A, and the reaction of a monophosphinic species for carbenoids (A and B). The most favored reaction channel is methylene transfer pathway for (PH3)Pt(CH2PH3)Cl2 (carbenoid B) species with a barrier of 31.32 kcal/mol in gas phase. The effects of dichloromethane, THF, and benzene solvent are investigated with PCM method. For carbenoid A, both methylene transfer and carbometalation pathway barriers to reaction become remarkably lower with the increasing polarity of solvent (from 43.25 and 52.50 kcal/mol for no solvent to 25.36 and 38.53 kcal/mol in the presence of the dichloromethane). In contrast, the reaction barriers for carbenoid B via the methylene transfer path hoist 6.30 kcal/mol, whereas the barriers do not change significantly for the reaction path of a monophosphinic species for carbenoids (A and B).