Multiple C−H Bond Activations in Corannulene by a Dirhenium Complex

The reaction of Re₂(CO)₈(μ-C₆H₅)(μ-H), 1 with corannulene (C₂₀H₁₀) yielded the product Re₂(CO)₈(μ-H)(μ-η²-1,2-C₂₀H₉), 2 (65 % yield) containing a Re₂ metalated corannulene ligand formed by loss of benzene from 1 and the activation of one of the CH bonds of the nonplanar corannulene molecule by an oxidative-addition to 1 . The corannulenyl ligand has adopted a bridging η²-σ+π coordination to the Re₂(CO)₈ grouping. Compound 2 reacts with a second equivalent of 1 to yield three isomeric doubly metalated corannulene products: Re₂(CO)₈(μ-H)(μ-η²-1,2-μ-η²-10,11-C₂₀H₈)Re₂(CO)₈(μ-H), 3 (35 % yield), Re₂(CO)₈(μ-H)(μ-η²-2,1-μ-η²-10,11-C₂₀H₈)Re₂(CO)₈(μ-H), 4 (12 % yield), and Re₂(CO)₈(μ-H)(μ-η²-1,2-μ-η²-11,10-C₂₀H₈)Re₂(CO)₈(μ-H), 5 (12 % yield), by a second CH activation on a second rim double bond on the corannulene molecule. The isomers differ by the relative orientations of the coordinated Re₂(CO)₈(μ-H) groupings. All new products were characterized structurally by single crystal X-ray diffraction analysis.     

Catalyst-Free Arylation of Tertiary Phosphines with Diaryliodonium Salts Enabled by Visible Light

The visible-light-induced arylation of tertiary phosphines with aryl(mesityl)iodonium triflates to produce the quaternary phosphonium salts occurs under mild, metal, and catalyst-free conditions. Photo-excited EDA complexes between diaryliodonium salts and phosphines supposedly enable this transformation, which is difficult to achieve through the traditional ground-state reactions. Demonstrating high functional group tolerance, broad scope, and complete selectivity of the aryl group transfer, the method is particularly compatible with sterically congested phosphines, which are challenging under metal-based catalytic methods.     

A Water-Stable Lanthanide Coordination Polymer as Multicenter Platform for Ratiometric Luminescent Sensing Antibiotics

As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors.     

K10Ga3Bi6.65 – The First Compound in the Ternary A-Ga-Bi System Comprising Cyclic Tris-meta Borate-Analogous [Ga3Bi6]9– Units and Bi2 Dumbbells

K₁₀Ga₃Bi_6.65 is the first representative in the ternary system A-Ga-Bi (A = alkali metal). It contains [Ga₃Bi₆]^9– anions with planar triangular-coordinated Ga atoms as the main structural feature, accompanied by isolated Bi–Bi dumbbells. Alkali metal cations are counterbalancing the charges and fill the space between the anionic units. According to the Zintl-Klemm concept charge balance is reached if an almost equal ratio of single and double-bonded Bi₂ dumbbells are present according to (K⁺)₁₀[Ga₃Bi₆]^9–([Bi-Bi]^4–)_1/6([Bi=Bi]^2–)_1/6.     

Structure and conductivity of AOT solutions in n-hexadecane-chloroform mixtures

The structure and conductivity of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) solutions (2.5 × 10⁻⁴–2.5 × 10⁻¹ M) in n-hexadecane-chloroform mixture at the chloroform concentration from 50 to 100 vol% were studied. The diffusion ordered spectroscopy NMR study revealed that in the indicated range, the observed hydrodynamic diameter of micelles depends only on the AOT concentration and does not depend on the chloroform content. Molar fractions of free AOT molecules and those aggregated into micelles were calculated using the Lindman's law: at concentrations above 2.5 × 10⁻¹ М, the solutions contain mostly the micelles, whereas at concentrations below 2.5 × 10⁻⁴ M, the solutions contain AOT molecules. The transition region contains both the AOT molecules and the micelles. Conductivity measurements were used to determine free charge carriers in the bulk of solutions and their contributions to conductivity.     

A Mechanistically and Operationally Simple Route to Metal–N-Heterocyclic Carbene (NHC) Complexes

We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds.     

Cyanine-Flavonol Hybrids for Near-Infrared Light-Activated Delivery of Carbon Monoxide

Carbon monoxide (CO) is an endogenous signaling molecule that controls a number of physiological processes. To circumvent the inherent toxicity of CO, light-activated CO-releasing molecules (photoCORMs) have emerged as an alternative for its administration. However, their wider application requires photoactivation using biologically benign visible and near-infrared (NIR) light. In this work, a strategy to access such photoCORMs by fusing two CO-releasing flavonol moieties with a NIR-absorbing cyanine dye is presented. These hybrids liberate two molecules of CO in high chemical yields upon activation with NIR light up to 820 nm and exhibit excellent uncaging cross-sections, which surpass the state-of-the-art by two orders of magnitude. Furthermore, the biocompatibility and applicability of the system in vitro and in vivo are demonstrated, and a mechanism of CO release is proposed. It is hoped that this strategy will stimulate the discovery of new classes of photoCORMs and accelerate the translation of CO-based phototherapy into practice.     

Polymerization of aniline in perfluorinated membranes under conditions of electrodiffusion of monomer and oxidizer

Journal of Solid State Electrochemistry - A series of composites based on the perfluorinated MF-4SK membrane and polyaniline was obtained under electrodiffusion of monomer and oxidizer. Aniline was...     

Humic-based bionanocomposites containing stable paramagnetic gold nanoparticles for prospective use in pharmaceuticals

Structural peculiarities and supramolecular organization of medicinally promising nanocomposites, synthesized from humic substances, which essentially differ depending on decomposition degree, have been studied using electron spin resonance, transmission electron, and confocal laser scanning microscopy techniques and some other modern physical–chemical methods. It is shown that stable zero-valent gold nanoparticle of about 10–17?nm in size are formed in a natural macromolecular matrix. The nanocomposites obtained turn out to be stable in aggregative state for a long time and preserve their properties that are extremely important for prospective medicinal substances.