Strong Coupling and Laser Action of Ladder‐Type Oligo(p‐phenylene)s in a Microcavity

We investigate the coupling of ladder‐type quarterphenyl to the photon modes of a dielectric ZrO_x/SiO_x microcavity at ultraviolet wavelengths. For a relatively long cavity (≈10 μm) with high‐reflectivity mirrors (0.998), optically pumped laser action is demonstrated in the weak‐coupling regime. We observe single‐mode operation with a threshold of 0.4 mJ cm^?2. Strong coupling is achieved by using a short λ/2 cavity. We find pronounced anti‐crossing features of the molecular (0,0) and (0,1) vibronic transitions and the cavity mode in angle‐dependent reflectivity measurements providing Rabi splittings of (90±10) meV. All these features occur spectrally resonant to the exciton transition of ZnO demonstrating the potential of ladder‐type oligo(p‐phenylene)s for the construction of inorganic/organic hybrid microcavities.     

Optoelectronic and Self‐assembly Properties of Porphyrin Derivatives with Click Chemistry Modification

A series of functionalized porphyrin molecules containing electron‐rich alkynes, synthesized by means of the Sonogashira coupling reaction were further modified by reacting the ethynyl groups with click reagent through a formal [2+2] click reaction. The photophysical and electrochemical properties of the porphyrin derivatives were studied by UV/Vis spectroscopy and cyclic voltammetry. We show that the optoelectronic properties are affected by the click reagent groups and central metal ions. The functionalized porphyrin molecules show strong charge‐transfer (CT) bands in the visible region (near‐IR region) and potent redox activities. Through a phase‐exchange self‐assembly method, the highly organized morphologies were observed by scanning electron microscopy (SEM). The functionalized porphyrin molecules represent an interesting set of candidates for optoelectronic device components. The effect of the metal ions or click reagent groups on the self‐assembly properties were also studied by the UV/Vis spectroscopic titration experiments.     

Qualitative spectroscopic characterization of the matrix–silane coupling agent interface across metal fibre reinforced ion exchange resin composite membranes

The characterization of novel metal reinforced electro-dialysis ion exchange membranes, for water desalination, by attenuated total reflectance Fourier transform infrared spectroscopy mapping is presented in this paper. The surface of the porous stainless steel fibre meshes was treated in order to enhance the amount of surface oxide groups and increase the material hydrophilicity. Then, the metal membranes were functionalized through a sol–gel reaction with silane coupling agents to enhance the affinity with the ion exchange resins and avoid premature metal oxidation due to redox reactions at the metal–polymer interface. Polished cross sections of the composite membranes embedded into an epoxy resin revealed interfaces between metallic frameworks and the silane layer at the interface with the ion exchange material. The morphology of the metal–polymer interface was investigated with scanning electron microscopy and Fourier transform infrared micro-spectroscopy. Fourier transform infrared mapping of the interfaces was performed using the attenuated total reflectance mode on the polished cross-sections at the Australian Synchrotron. The nature of the interface between the metal framework and the ion exchange resin was shown to be homogeneous and the coating thickness was found to be around 1 μm determined by Fourier transform infrared micro-spectroscopy mapping. The impact of the coating on the properties of the membranes and their potential for water desalination by electro-dialysis are also discussed.     

Impact of titanate coupling agent on properties of high density polyethylene composite filled with coal gangue

In this study, surface modification of coal gangue (CG) was performed with titanate coupling agent 201 (isopropyl tri(dioctylpyrophosphate) titanate), and the effects of surface modifier on mechanical properties and thermal stability of high-density polyethylene filled with CG (HDPE/CG) and high-density polyethylene filled with modified CG (HDPE/mCG) composites were investigated. The coupling agent was successfully grafted on CG surface through chemical reaction according to the analyses of Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), and the coupling agent can effectively enhance the hydrophobicity of surface that was verified by water contact angle beyond 90° of modified CG sample. With the introduction of coupling agent, some enhancements of tensile strength, flexural strength, and impact strength were observed in HDPE/mCG compared with HDPE/CG, due to the improved compatibility between mCG fillers and matrix. The increased storage modulus and decreased loss factor of HDPE/mCG composite further confirm the stronger interface adhesion after modification. Moreover, it is found that titanate coupling agent 201 can improve the thermal stability of HDPE/mCG composite to some extent.     

PyCDFT: A Python package for constrained density functional theory

We present PyCDFT, a Python package to compute diabatic states using constrained density functional theory (CDFT). PyCDFT provides an object-oriented, customizable implementation of CDFT, and allows for both single-point self-consistent-field calculations and geometry optimizations. PyCDFT is designed to interface with existing density functional theory (DFT) codes to perform CDFT calculations where constraint potentials are added to the Kohn–Sham Hamiltonian. Here, we demonstrate the use of PyCDFT by performing calculations with a massively parallel first-principles molecular dynamics code, Qbox, and we benchmark its accuracy by computing the electronic coupling between diabatic states for a set of organic molecules. We show that PyCDFT yields results in agreement with existing implementations and is a robust and flexible package for performing CDFT calculations. The program is available at https://dx.doi.org/10.5281/zenodo.3821097 .     

Synthesis of selenium-containing biindolyls and their Diels–Alder reaction toward the synthesis of heteroannulated [a]- and [c]-carbazoles

We reported the first syntheses of 2- and 3-(2-(benzo[b]selenophen-2-yl)-indoles and their Diels–Alder reactions to furnish six unique annulated benzoselenphene carbazoles. This facile route can be used to synthesize selenium-containing biindolyl derivatives that possessed potential pharmaceutical activities.     

Synthesis of a C(sp2)-bridged Phosphine-Borane by Ionic Coupling

The vinyl carbenoid H₂C=CBr(Li) has been used as key precursor to prepare a geminal C(sp²)-bridged phosphine-borane. Starting from bromoethene, two sequences of lithiation/electrophilic trapping, with ClPiPr₂ and FBMes₂ respectively, affords iPr₂P–C(=CH₂)–BMes₂ 3 [Mes = 2,4,6-(H₃C)₃C₆H₂]. This new phosphine-borane 3 was characterized by multi-nuclear NMR and mass spectroscopy. It adopts a monomeric open structure without P→B interaction. A few crystals of a secondary product 4 were analyzed by X-ray diffraction, revealing an unusual dimeric structure.     

Enantioselective Synthesis of a Tricyclic,sp3-Rich Diazatetradecanedione: an Amino Acid-Based Natural Product-Like Scaffold

6-, 7-, and 8-membered rings are assembled from a linear precursor by successive cyclisation reactions to construct a tricyclic diazatricyclo[6.5.1.0^{4, 9}]-tetradecanedione scaffold. Advanced building blocks based on d -aspartic acid and l -pyroglutamic acid were combined by a sp³−sp² Negishi coupling. A carbamate-guided syn-diastereoselective epoxidation followed by an intramolecular epoxide opening allowed the construction of the piperidine ring. An efficient one-pot hydroxyl-group protection twofold deprotection reaction prepared the ground for the cyclisation to the bicycle. A final deprotection of the orthogonal protecting groups and lactamisation led to the novel, sp³-rich tricycle. The final compound is a substrate mimic of peptidyl-prolyl cis-trans isomerases featuring a locked trans-amide bond. Cheminformatic analysis of 179 virtual derivatives indicates favourable physicochemical properties and drug-like characteristics. As proof of concept we, show a low micromolar activity in a fluorescence polarisation assay towards the FK506-binding protein 12.     

光催化甲烷转化研究进展

甲烷催化转化为高附加值产物、实现甲烷高效利用,具有重要的研究意义及工业应用价值。长期以来,如何在较温和的条件下将甲烷转化为其它更有价值的有机衍生物,如醇、芳烃、长链烷烃和烯烃等,是催化、化学及化工领域的热点和难点课题之一。光催化反应由光能激发产生光生电子和空穴,参与到甲烷C―H键活化和自由基形成,这为低温甲烷转化提供新的途径,本文主要围绕甲烷氧化和偶联反应,总结了近年来光催化研究进展,并对如何进一步提高光催化性能提出展望。     

Terminal Alkyne Coupling Reactions Through a Ring: Effect of Ring Size on Rate and Regioselectivity

Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C₂H₄)][BAr^F₄] (n=12, 14, 16; Ar^F=3,5-(CF₃)₂C₆H₃)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu₂C₆H₃) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH₂)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C₂H₄)][BAr^F₄] and solvent effects.